Transition metals in organic synthesis: Hydroformylation, reduction and oxidation

333

TRANSITION

METALS

IN ORGANIC

SYNTHESIS:

HYDROFORMYLATION,

REDUCTION

AND OXIDATION

ANNUAL SURVEY COVERING

THE YEAR 1984x

LASZLd MARK6 Institute of Organic Chemistry, H-8200 Veszprem,

University

of Veszprbm,

Hungary

CONTENTS I. Theoretical

335

Calculations

II. Hydroformylation 1. Hydrogenation

and Related Reactions

of CO to Hydrocarbons

336

of CO

and Oxygen-containing 336

Organic Compounds

337

2. Hydroformylation a) Co Catalysts

337

b) Rh Catalysts

338

c) Other Metals

340

d) Heterogeneous e) Modified

Systems

342

(Supported Complexes)

343

Hydroformylations

3. Homologation

of Alcohols,

Carboxylic

Acids and Esters 344

with CO + H2 4. Coordination

Chemistry

Related to Cb Hydrogenation

and 345

Hydroformylation 5. Water Gas Shift Reaction

347

6. Reduction

346

with CO + H20

7. Miscellaneous III. Hydrogenation

Reductive

Transformations

of CO and CO2

350

and Reduction

350

1. H-D Exchange 2. Hydrogenation

349

351

of Olefins

a) Fe and Ru Catalysts

351

b) Co, Rh and Ir Catalysts

352

c) Ni, Pd and Pt Catalysts d) Other Metals

356

x- Previous review see No reprints

J.

organomet.Chem.,

357 283(1985)221-337.

available.

Referencesp. 435 0022-328X/86/$03.50 0 1986ElsevierSequoiaS.A.

334 3. Asymmetric

of Olefins

357

and Alkynes

363

Hydrogenation

4. Hydrogenation

of Dienes

a) Fe, Ru and OS Catalysts b) Co and Rh Catalysts

363

c) Pd Catalysts

365

d) Other Metals

366

364

of Arenes

6. Hydrogenation

of Carbonyl

7. Hydrogenation

of Nitro Compounds

369

Hydrogenations

370

8. Miscellaneous 9. Coordination

Chemistry

and Heterocyclic

366

5. Hydrogenation

compounds

367

Compounds

Related

370

to Hydrogenation

372

10. Dehydrogenation 11. Hydrogen

Transfer

314

Reactions Donors

374

b) Hydrogenation

of C=C Bonds

374

c) Hydrogenation

of C=O Bonds

376

a) Alkanes

as Hydrogen

d) Hydrogenolysis 12. Reduction

by Hydrogen

without

Molecular

378

Transfer

378

Hydrogen

a) Transition

Metal Hydrides

378

b) Low Valent

Transition

379

c) Inorganic

Reductants

Metal Complexes in the Presence

of Transition

Metal 380

Complexes d) Reduction e) Organic

of Carbonyl

Reductants

Compounds

via Hydrosilylation

in the Presence

of Transition

Metal 384

Complexes

385

f) Electroreduction

386

IV. Oxidation 1. Catalytic

383

Oxidation

of Hydrocarbons

or Hydrocarbon

Groups 386

with O2 a) General

386

b) Oxidation

of Alkanes

386

c) Oxidation

of Olefins

387

of Olefins

388

of Aromatics

389

d) Epoxidation e) Oxidation 2. Catalytic

Oxidation

of O-containing

a) Oxidation

of Alcohols

b) Oxidation

of Phenols

c) Oxidation

of Aldehydes

d) Miscellaneous

Functional

Groups with 02391 391 392

and Ketones

Oxidations

395 397

335 3. Catalytic

Oxidation

of N-containing

Organic Compounds 397

with O2 4. Catalytic Organic

of P-, S-,or Halogen-containing

Oxidation

Compounds

5. Catalytic

Oxidation

Inorganic

400

with O2 of Organic

Compounds

with Organic or 402

Oxidants

a) Oxidation

of Hydrocarbons

b) Epoxidation

or Hydrocarbon

402

Groups

404

of Olefins Groups

410

Organic Compounds

413

c) Oxidation

of ,O-containing Functional

d) Oxidation

of N-containing

e) Oxidation

of P-, S-,or Halogen-containing

Organic 414

Compounds 6. Stoichiometric Vale&

Oxidation

Transition

a) Oxidation

of Organic Compounds

415

Metal Complexes

of Hydrocarbons

b) Epoxidation

with High

or Hydrocarbon

415

Groups

418

of Olefins

c) Oxidation

of O-containing

Functional

Groups

419

d) Oxidation

of N-containing

Organic Compounds

424

e) Oxidation

of P-, S-,or Halogen-containing

Organic 427

Compounds 7. Coordination

Chemistry

428

Related to Oxidation

429

8. Electrooxidation V, Reviews

430

List of Abbreviations

433

Metal

433

Index

435

References I. Theoretical

Calculations

Results of CO hydrogenation correlated structure

on supported

with results of EHMO calculations of Rh4(CO)12

The breaking both discrete

was studied by orbital Reaction mechanisms

[ll. metal

complexes

analysis

and the extended

of the oxidative

elimination

and on Ni and Ti surfaces

addition

Rh-phosphine

complex-catalyzed

nes has been studied by EHT MO calculations. a dihydride-type

Referencesp.435

intermediate

Hiickel method

[21.

of H2 to Pt(CH3)3

of CH4 from Pt(H)(CH3)(PH3)2

studied by ab initio RHF and CI calculations the cationic

were

of the H-H bond in H2 and a C-H bond in CH4 on

transition

and the reductive

Rh catalysts

of the electronic

were

[31. The mechanism hydrogenation The results

[41. MO calculations

of

of alkesupport

of H2Rh(C2H4)C1L2

Ph3P), a species directly

(L = substituted catalytic

hydrogenation

substituents

by Wilkinson's

of H2Rh(C2Hq)X(PH3)2

with experimental

by Br- favors hydrogenation A theoretical -peroxide

bonding

metal-bound

complexes,

have little effect on the kinetics

tion. EHMO calculations agreement

involved

observations

indicate

that the

of the hydrogena-

(X = Cl,Br) show in

that substitution

of Cl-

[5].

model was provided in peroxo-metal

that describes

complexes

"peroxy anion" can readily

philic alkenes

in homogeneous

the metal-

and explains why the

transfer

oxygen to nucleo-

[6].

See also [223].

II. Hydroformylation 1.

Hydrogenation Organic

and Related Reactions

of CO to Hydrocarbons

and Oxygen-containing

Compounds

The reduction

of CO to methane

by sodium amalgam

+ PhOH. The actual catalyst

by Cp2vC12 surface [7]. The liquid-phase Co(acac)2

carbons with 85% selectivity Homogeneous preferentially

to olefins

beneficial

formate.

by Ir4(C0j12 as solvent

while phosphines

to methanol.

selectivities

in

(H2:C0 = 1:l) producing

In n-pentane

promoters

effect on the selectivity

hydro-

[81.

at 250°C and 2000 bar

MeOH and methyl

gave rise to increased

produced

of CO is catalyzed

amines were found to be effective

is catalyzed on the amalgam

of CO at 260°C with

in THF-tetralin

hydrogenation

of solvents

is vanadocene

hydrogenation

+ LiAlH4 as catalyst

a variety

of Co

had a

Halide promoters

of C2-products

[91. Synthesis

gas (H2.-CO = l-2:1) is converted to esters at lOO-230°C and 250-400 bar using homogeneous Ru + Rh catalysts (ratio l-10:2) containing halide promoters

in AcOH as solvent

alcohols

and esters

catalyst

in molten

from synthesis

gas with a RUDER

Bu4PBr has been investigated

yields of ethanol were achieved Most of the Ru and Co present accounted

[lo]. The production

+ Co2(CO)8

in detail.

at Ru/Co ratios between

in the reaction mixture

for on the basis of the species Co(CO)i,

follow the Schultz-Flory

distribution

which

that the Cl and C2 fractions

Highest

1 and 2.

could be

HRu3(CO)il

Ru(C0j3Br3. There was no direct spectroscopic evidence formation of mixed-metal carbonyls. The Cl-C3 alcohols other evidence,

of Cl-C3

and

for the did not

is in accordance are coming from

with

337 different

catalytically

active

intermediates

111,121.

2. Hydroformylation a) Co Catalysts High pressure

IR and W

measurements

nism of the hydroformylation

confirm

of 1-octene

the Heck mecha-

and cyclohexene

with

C02(CO)8 as the starting catalyst. The reaction between the acylcobalt carbonyl RCOCo(CO)4 and H2 has been found to be the major pathway

at 80°C and 95 bar (CO:H2 = 1:l) whereas

reaction

between

The activation

RCOCo(CO)4

of the catalyst

step of the reaction aldehydes isomers

resulting olefins

and at the carbon carbon

has been determined.

product

[14]. A mathematical

tor was described Cracking, formation presence

accompanied

hydroformylation

ketones

See also

was performed

simultaneously

than without

Referencesp.435

electrolysis

of isobutene

as catalysts

of di-

with

of ethene or

phosphine

with HCO(CO)~

catalysts [171.

or

electrochemi-

The amount of catalyst

and the induction

period were

[181.

hydroformylation

has been studied.

in the order

[20,38,39].

The yields

synthesized

anode in the autoclave.

in the

and PR3 (R = Ph,

+ ditertiary

for the same conversion

ters decreased

COAX

[16]. Hydroformylation

of olefins

The kinetics clusters

reac-

and formate

(C5 and C,) at the expense of aldehydes

as catalysts

from a cobalt

smaller

hydroformybubble

of dicyclopentadiene

comprising

C02iCOJ8 propene with CO + H2 and COAX

necessary

for propene

did not exceed those obtained

alone as catalyst

tally

at the terminal

in a packed

or pentaphenylphosphole.

cyclopentadienedimethanol

HCO(CO)~PBU~

model

carbon

did not vary greatly

aldol condensation,

systems

Bu, Me, or cyclohexyl)

Hydroformylation

in the

[15].

hydrogenation,

of catalyst

gave mainly

of the 42 octene

reaction

catalyst

of all Cg

at the tertiary

distributions

lation with a cobalt-phosphorous

pathway.

is the slowest

Me groups

hydroformylation

near to it, promoting

atoms. Aldehyde

with conversion

COAX

distribution

from the hydroformylation

inhibited

the alternative

is only a minor

precursor

[13]. The relative

using HCO(CO)~

branched

and HCo(C0)4

R = Pr>H

with RCCO~(CO)~

The activity

>Ph>EtOOC

>Cl

of the clus[191.

338 b) Rh Catalysts Hydroformylation conditions

mild

(25-50°C,

co,$_nmn(‘O) 12

phosphine

the mixed-metal

but this effect nated

as catalyst

or preformed

or phosphite;

disappeared

clusters

n = 0, 2,0r 4; x = l-4). the highest

with time and the complex

clusters.

under

precursors

Rh4fCO)l2_xLx

n = 2 showed

clusters,

into homometallic

has been investigated

1 bar) using

+ L systems

(L = tertiary Among

of some olefins

According

activity

disproportio-

to IR spectroscopy

if

L = phosphite,

all Rh was in the form of Rh4(CO)QL3

but if

L=

fragmentation

could be ob-

phosphine,

served

1203. l-Pentene

tions also with Rh4(CO)12 combined ligand

addition

resulted

Increase

to dinuclear

complexes

was hydroformylated +x.PPh2H

under the same condi-.

+y'L catalyst

systems.

of PPh2H and the trisubstituted

in a synergistic

of x to 3 or 4 caused

effect

The

phosphorous

for x = l-2 and y = 2-4.

a sharp drop in catalytic

activity

E211. Hydroformylation

of 1-hexene

or Rh(AA)EP(OPh)312

has been examined.

increased

rate and selectivity

study of Ph3N,

Ph3P, Ph3As,

(AA = 8 -diketone

or Ghydroxyor phosphite

of the reaction

hydroformylation

H2/C0

that regiospecifity,

showed

varies

conversion inhibited

inversely

to aldehyde

Rh2(COD)2C12

phino

alkanes

terminal

which

olefins

The influence Rh(CO)(PPh3)2Cl very

has been

1261. In the hydroformylation

aldehyde

increases

CL,W-bis

diphenylphos-

with

of substituted

has been discussed N-heterocycles

[251. and

of propene

catalyzed

by

N-containing

compounds

with

selectivity

of allyl-

showed

formation

amino acids,

investigated.

increased

Ph3Bi

small conversions

tne hydroformylation

on the hydroformylation

low basicity

with Ph3P, while

60°C and 5 bar CO + H2

a Rh + PPh3 catalyst

of 32 amines,

The maximal

(n = l-4) as catalyst

[24]. The role of

promote

with

urea derivatives

.at

for linear-aldehyde

ratio

by the n/i product

ligand basicity.

and Ph3N gave very

of 1-heptene

that the selectivity the phosphine/Rh

as measured

and Ph2P(CH2),PPh2

in the

at 90°C and 8 bar of

(87-95%) was obtained

[23 1. Hydroformylation using

of dodecene-1

to increased

hydroformylation

[221. A comparative

Ph3Sb and Ph3Bi as ligands

Rh-catalyzed ratio,

of Rh(AA)fCO)(PPi-$

An excess of phosphine

type complexes

quinoline)

in the presence

and the nJi ratio

(estragole,

safrole,

euge-

(anethole, isosafrole, isoeugenol), as well as propenylbenzenes nol) to the corresponding aldehydes at 5 bar pressure and 80°C the catalyst

precursor

Rh2( 11-SCMe3)2(C0)2[P(OMe)3]2

proved

to be more

339

selective than HRh(CO)[PPh313. zation of allylbenzenes catalyzes

The latter caused extensive

[27]. The heterobimetallic

the hydroformylationof

The analogous

(2)

complex

is

isomeri-

complex

(1)

1-hexene at 80°C and 5 bar CO+H2.

somewhat less active which is attrib-

uted to the Zr center inducing more electron density on the Rh [28].

atoms

tyu

tpl

. \Rh/5q.+hfco \ / Ph2P oc

1, x = cP2zr:

2, x = --CH2+-

PPhP

\ c*-X-CH{

Glycols are produced by hydrofonnylating

vinyl acetate or

ally1 acetate with Ph complexes as catalysts at 70-150°C to AcOCH2CH2CH0

and AcOCHMeCHO

which may be converted

respectively, diols

or AcOCH2CHMeCH0

[29]. Several homoallylic

and AcOCHEtCHO,

to the corresponding

alcohols

alkane-

(3) were hydroformylated

with a Rh+PPh3 catalyst and the resulting aldehydes oxidized with pyridinium yields

chlorochromate

to give

6-lactones

(4) in excellent

[30]. H

-4

R

R

-___c

i

0

3 (El-N-propenylphthalimidine hydroformylated

Q

4

with HPh(CO)(PPh3)3

(811 catalysts. With

(5) and N-allylphthalimidine

were

+ (-)-DIOP (7) [or (-)-DIOCOL

(5) as substrate complete regioselectivity

to

(6) was achieved but the ally1 compound yielded both possible aldehydes

in roughly equal amounts. Practically

tion was observed

no optical induc-

[31]. 0

NJ-0

5

References p. 435

Cl-IO

-

N 0

6

-c

340

Me2C

r

x

I0 ‘0

PPh2 PPh2

z21B

7,

(-)-

DIOP

(-)-

8,

.The potentially

tridentate

in the form of RhCl(CO)(L) hydroformylation

Ii

H

H

ligands

complexes

of olefins.

(9) were prepared

(L = 9) as catalysts

The catalysts

40°C, but those ligands which contained ineffective

in providing

asymmetric

DIOCOL and used for the

were active even at

a chiral R group were

induction

in the hydroformy-

[32].

lation of styrene

9,

R = Me, Et, m-Bu,

(S)-(-)-2-methyl-

1-butyl, menthyl

The homogeneous = Ph2P(CH2)2N+Me3], showed catalytic

catalyst prepared

activity

lation in a two-phase catalyst phines

for alkene hydrogenation

PhMe as solvent by extracting

See also

Ph2PCH2COONa

for the hydroformylation

the HRh(CO)(PPh3)3

and hydroformy-

[331. The homogeneously dissolved Rh from hydroformylation reaction products

like P(C6H4S03Na)3,

apparatus

[amphos

system

was regenerated

containing

[(NBD)RhCl(amphos)lN03,

from amphos nitrate and I@IEJD)R~C~I~

catalyst

with water-soluble or PhP(CH2COONa)2

phos1341. An

of ethene to EtCHO and recycling

was described

1351.

[199].

c) Other Metals Hydroformylating as catalyst HFe(C0)2Cp

propene

at lOO-150°C

has been detected

taken from the reaction ed under such conditions

in toluene

solvent with Cp2Fe2(C0)4

and 70-140 bar CO + H2 the complex by infrared

mixture.

About

spectroscopy

in samples

35% of the dimer is convert-

to the hydride which probably

plays a

341 similar system

role in the catalytic [36].

Heptyne-1

and -2 and heptene-1

and hydrogenated Ir(L)(COD)(PPh3) in the presence cyclohexene mixed

or [Ir(L)(COD)12 of PPh3

revealed

observed Co alone styrene

or Ru3(C0)12

in Ru. A similar metal

cluster

+ Fe3(C0)12

[38]. The mixed metal

mixed

FeCo3(C0)i2 catalysts

clusters

conditions

intact and could times were used

but the other

be recovered

fragments

either

or the formation

11

See also

[163].

Referencesp. 435

was used as catathan

have been tested (at 130°C) under

remained Rather

and the

apparently

long reaction

a very low catalytic of very small amounts

acof

[391.

(CO13

CP

is first order

to Co2(COj8

five clusters

Kinetic

were not better

(lo)-(15)

with high yield.

(l-6d) suggesting

tivity of the clusters

+ Ru3(C0)12

effect was also

of pentene-1

(15) decomposed

of

alone.

formation

synergistic

for the hydroformylation

(at 7OOC). Cluster

reaction

(L = pyrazolate)

on using Co2(CO)9

with COAX

that the rate of aldehyde

if the mixed

as catalysts

(H2:C0 = 1:l) using

as catalysts

increased

compared

lyst, but Co2(CO)9

hydrofomylated

were partially

[37]. The rate of hydroformylation

was greatly

catalysts

studies

at 140°C and SO bar

in Co and 0.6 order

active

in the Co-catalyzed

cycle as HCo(C0)4

(co)2[P(OMu)3] 12

342 d) Heterogeneous Complexes prepared

Systems

of Co2(CO)S

(Supported Complexes)

with phosphinated

and tested as catalysts

pene at lOO-170°C were determined

under CO pressures

[Co,(CO),,]( k4-PR)2]

of 0.3-10 bar. Rate constants

(R = polystyrene

to heptanals

- divinylbenzene

phenylphosphide

on polymer crown ether

copolymer)

the hydroformylation

with 83% conversion

The same tetranuclear formylation

of pro-

[40]. The supported metal cluster catalyst

having a Co content of 9.5% catalyzed 1-hexene

silica gel have been

for the hydroformylation

of

and 100% selectivity

Co carbonyl

cluster

[411.

supported

(16) was found to be more active for hydro-

of terminal olefins then when the cluster alone was

used as a homogeneous

catalyst

[42].

CH2

m2

x3-

i n

t

0 16

Molecular prepared

sieve-enclosed

rhodium carbonyl

and used for the hydroformylation

catalysts

of aliphatic

130°C and 85 bar synthesis gas 1431. Simultaneous hydrogenation

and hydroformylation

and Y zeolites

in a reactant

(3:3:2:1)at atmospheric aldehyde

resulted

showed the presence

in butyraldehydejisobutyr-

It was concluded,

can catalyze

After hydroformyl-

of Rh6(CO)16

Y [441. Ethene and propene were hydroformylated catalyst.

X

of propene:H2:N2:C0

ratios of 2.0/l and 1.911, respectively.

ation IR spectroscopy

at

vapor-phase

of propene over Rh-exchanged

stream consisting

pressure

were olefins

on zeolite

over a Rh-Y-zeolite

that the active sites at the surface

the hydroformylation

of both substrates

but that the

active sites formed in the pores even at a very short distance from the entrance can catalyze only the hydroformylation 1451. The rate of EtCHO formation a Rh-Y zeolite at atmospheric mately

proportional

+o

of ethene

in ethene hydroformylation

over

pressure was found to be approxi-

ethene partial pressure

and proportional

343

to the square formation no isotope instead

root of H2 partial

decreased effect

on the reaction

the rate of aldehyde

pressure

increased.

rate was observed

using

Almost D2

of H2 [461.

Gas-phase

hydroformylation

Pd-exchanged

silica catalysts

Best results

were obtained

ic supports amounts

pressure;

as the CO partial

with

e) Modified

formed

were

over

psessure. strongly

found unsuitable.

acid-

Only minor

[47].

Hydrofonnylations

The Co2(CO)8

+ dppe catalyst

of olefins

RCH=CH2

has been performed

silica gel supports,

like silica-alumina

of ethane were

formylation

of ethene

at 70°C and atmospheric

system catalyzes

with CO + H20 resulting

+ 2C0 f H20

the hydrocarbonylation

-

RCH2CH2CH0

of olefins

the hydro-

in aldehydes:

+ CO2

with CO + H20 resulting

in

ketones: 2RCH=CH2

+ 2C0 f H20

the hydroformylation ation of propylene CH$H=CH2

Highest

catalytic

formation Propene

byproducts

of olefins

432

found around

P:Co = l:l. Ketone ratios

*acids and dipropyl phosphines

[481.

ketones

give catalysts

as with

[SOI.

ketoneswere CF3COOH

as catalysts.

Referencesp.435

C3H7CH2N

at high olefin:Co

butyric

ditertiary

activity

CO and H2 in aqueous

were

reaction

butanols,

5% water

with CO + H2 and the aminomethyl-

2 CO + H20 -

activities

C5 or C7 dialkyl

of about

RC2~4f 2co + co2

3

[491. Other

lower catalytic

complexes

l

is the main

yields

(

with CO + H20:

HN 3

l

-

formed

solutions

Reaction

in the solvent

from ethene

at SO-70°C with

rate was highest [511,

or propene, Pd(II)-

PPh3

in the presence

344 3.

Homologation

of Alcohols,

Carboxylic

Acids and Esters with

CO + H, Homologation

of methanol

to acetaldehyde

CH30H + CO + H2 can be performed

-

CH3CH0

with Co(OAc)2. 4H20 + 12 as catalyst at 140°C and

300 bar. Cyclic ethers and glymes have a beneficial selectivity converted

of the reaction.

to acetaldehyde

selectivity

In tetraglyme,

effect on the

for example, MeOH is

with nearly 100% conversion

and 86%

[52]. The kinetics of the reaction has been studied

using a CO(OAC)~ for methanol,

+ PPh3 + Me1 catalyst. A first order dependence

an order of 2 0.4, for Me1 an order of 2 and for PPh3 an order of -2 was established.The

cobalt acetate and CO was found. For H

oxidative

addition of Me1 to a Co species is regarded

as the rate determining

step [531. Addition

CO(OAC)~. 4H20 + LiI catalyst of the platinum

of PtC12 to a

increased the reaction rate. The role

is to accelerate

the reduction of Co 2+ to Co(CO)-4

1541. The homologation

of methanol

to ethanol has been investigated

using the "supported liquid phase catalyst" method with RuC12(C0)2(PPh3)2

+ Co12 + NaI + PPh3 as catalyst

and 100-200 bar. Carbowax as support. Unusually [55]. Synthesis

1500 was used as solvent and Chromosorb

high selectivities

formation were obtained

of ethanol

(and propanol)

and no ethers were observed as byproducts

of ethanol in tetraglyme

vent with CO(OAC)~.~H~O,

system at 180_2OO?J

Ru(acacj3

or a cyclic ether as sol-

and I2 as catalyst was performed

in two stages. First at 140°C acetaldehyde

was produced and then

hydrogenated

to 2OOOC. In this way

by increasing

the temperature

over 85% yield was obtained tridentate

phosphines

[56]. The novel, potentially

ligands with a CO(OAC)~.~H~O system at 155-200°C

I

+ RuC13.3H20

+ I2 (or MeI) catalyst

and 300 bar CO + H2. Best MeOH conversion

70% and EtOH selectivity

Ph2P I-J 0

bi- or

(171, (18) [57] and (19) [58] were used as

c-JO

was

40%.

CH2-Lh-CH2JJ

OX-!-X0

R=Me, tBu, Ph 17

18

19 X=CH2, 0, NH

345 Propionic

form

alkyl

430 bar. ently

acid

propionate

The

long

with

CO/H2

of ruthenium

times

higher

the

at 200°C

and

iodide

of the molecules

take

homologous

and

coreagents

methyl the

acids and

acetate

acetate

to C2 products

or piperidine

have

Coordination Chemistry -Hydroformylation

for

the homogeneous

examination

intermolecular sion

of metal The

of model

under

hydroformylation

copy.

At

form

80°C

of

and

q3-C4H7Co(C0)3.

complex

is incomplete

hydroformylation n2 was

studied

under

Kinetic

data

cal

syn-gas

for

dominantly by CO

lead

are

Water

of

of

decreases

as pyridine

and

HMn(CO)5

involved

or HRu~(CO)~~I that

intra-

and

in the conver-

[62].

carbonyls

in the presence

has

been

studied

is mainly

of butadiene

by IR spectrospresent

in the

solution the formation of this + the remaining H and Co(C0); catalyze

The

high

formation pressure

of zfC0(C0)~ from with

to the conclusion

via

of

effect

In methanol

reactions

formed

The

such

of CO show

CO + H2 cobalt

and

[63].

tested.

[i.e.

paths

acyl

[611.

systems

conditions

95 bar

the

to CO HydsEtion

to formyls

of cobalt

Hydrogenation, and

homologation

N-bases,

reduction

transfer

hydrides

chemistry

has been

Related

in the presence

[60].

Ru-catalyzed

[59).

esters

of derivatives

is formed

effect

catalytic

hydride

the alkyl

whereas

a beneficial

4.

The

in the

and

at suffi-

acid

pressure

A mixture

to

predominant

as catalysts.

on both

220°C

but

becomes

in the

catalyst

are

carboxylic

bar

alcohols

ligands

to ethyl

selectivity

ester

place.

salt

propionate

weight

systems

higher

(CO:H2 = 1:l)

conditions

150-200

homologation

moiety

some

ethyl

and

gas

phosphonium

is methyl

molecular

carbonyl

carbonylation

synthesis

Reaction

product

reaction and

with

+ quaternary

esters.

primary

Formic react

reacts

of a RuO2. xH20

presence

catalyzed

and

IR and UV spectroscopy.

that

under

by HCO(CO)~

an associative

COAX

pathway

the

conditions

the hydride

which

is not

typiis pre-

inhibited

[641. The reaction

W~(~2)4~(~)4 proceeds mechanism

by second was

of the acyl

References p.435

+ Hco(cO)4--t order

proposed

compound

kinetics

which followed

CH3(CX2)4CHY+ Q2(C0)8 and

involves

is not the

retarded

fast

by H abstraction

by CO. A

reversible from

homolysis

the hydride

in

346 step. The

the rate-controlling chiometric olefin

hydroformylation

distribution

the concerted genation

formylated

Labeling

complex

results

of ~~o(~O~~

(C2H4)mCon.

complexes

ambient

for 1-alkene

and activity

partial presence tions

varies

synthesis products under

gasf

a la-

CO and H2 to and reduc-

carbonyl

Catalyst

at the X or

bound

to phos-

beads was recorded at different

species

and H~(CO)~~PPh3~2.

of.tbe

at

of H2

hydride.

took place under

at

CO

were observed

An increase

the concentration

hydroformylation

hydride

to n*ehydes.

if R is branched

Two predcminant

increased

In the

the condi-

1701. under hydroformylat~on in the presence

were ArH, ArCHO

these conditions

triphenylphosphines conditions

were

and ArCH20H.

during

wkth RRh(CO)tPPh3)3

Tributylphosphine

low-pressure

catalyst.

found

(200°C, 300 bar

of Rh, Co or Ru carbonyls.

[71]. Triphenylphosphfne

into propyldiphenylphosphine formYlation

of

of HRh(CO)(PPh3f3

The P-C bonds of p-substituted to be cleaved

K generates

and 18 bar CO + H2 pressure,

a dimer

of I-hexene

employed

the H

stable and act as rever-

hydroformylation

vilely

pressures.

pressure

HfB(cz))q

formed

of ethene

of reactive

polystyrene-divinylbenzene

temperature

CO:H2 J 0.67:1,

Under

of

and the other H

Addition

are highly

[69]. The IR spectrum

gel-form

and H2 partial

and HCo3(C0)9.

with ethene at77

sj.blereservoirs fox the generation

position

hydro-

in the presence

in the hydroformylation

H~~CO~(PPh~R~3

@

type Co carbonyl

’

tion of CO [68].

phinated

as hydro-

[671:

bile cobalt-ethene

stability

conformation

show that in the aldehyde

of Co atoms

intermediates

n-ally1

is no reaction

The CocondensatSon this complex

and 2,3-di-

starts with

to the s-a

group has come from HCo(C0)4

atcxa from HCo3(C0)9

and the

is staichiometrically

a mixture

there

experiments

atom of the formyl

of the

and -2 are formed

along with acyl and

at -l!S°C with

HCO(CO)~

The reaction

butene-1

3,3-D~ethy~butene

the same conditions alone.

that in stoi-

m-complex&ion

of the hydride

2,3-Dimethyl

E661.

suggest

between

was investigated.

l,&-addition

products

complexes

the initial

of the reaction

methyl-1,3-butadiene of the diolefin.

data

is the slow step 1651. The kinetics

with HCo(CO)3

product

kinetic

Main

was stable

is converted propene

The reaction

slowly

hydro-

starts with

347

the reversible

oxidative

to Rh. In the absence

addition

of CO .(hydrogenation

tion of propyldiphenylphosphine 8 transition

metals

catalyze

is much

under

-17OOC.

an induction

Following aryl-propyl

The kinetics

CO and H2 (Annual system,

Survey

the product

Water

Kinetic

being

With

[73].

reaction

of MeR3N+

cations

in terms of its rela-

homologation

of methanol to ethanol with 19B2, ref.53,54). In case of the manganate

selectkvity(

studies

Ru3(C0j12

and M(CO)6 favored

shift reaction

ethanol

vs. methane)

was indepen-

C:741.

with the water

to .&he associative

catalyzed

between

Me2P-

investigations

is first order

one

with path

[751. The water

in alkaline

by Ir4(C0)12

gas

2-ethoxyethanol

in base and in Ir, and zero order

step of the catalytic

cycle

OH- and HIr4(C0 ,I1 176 1.

PMe2

Me2pvPMe2

-2co2 / 2 H2d bw$‘/o2,,~ I

”

/I’d /‘----Pd H I M4p_Pm

Referencesp.435

catalyst

(M = Cr.;,MO, W) showed the dissociative

relative

/water,solution

gas shift reaction

as well as previous

in CO. The rate determining reaction

of

at 120-

Gas Shift Reaction

precursor, Fe(CO)5

group

Co was the most active.

was investigated

dent of H2 or CO pressure 5.

the forma-

aryl scrambling

were also formed

of the st0ichiometric

to the catalytic

bond

E721. Several

of H2 and propene

period

phosphines

and Mn(CO)i

with HFe(CO)q tionship

an atmosphere

conditions)

faster

intermolecular

triarylphosphines Rhmixed

of the phenyl-phosphorus

I I

‘H

is the

348 The dinuclear catalytically

complex

active

dissolved

in water

is

at 77OC and 1 bar. The actual

catalyst

is

(20) formed by reversible of CO. The catalytic

Pd2Clz(dmpm)2 substitution

cycle suggested

of Cl- by OH- and uptake shown on the preceed-

1771 is

ing page. The ruthenium phine

ligands,

catalyze

carbonyl

complexes

Ru(C~)4(PPh2C2H4-SIL)

the water

anchored and

gas shift reaction

is about one order of magnitude

nuclear

one

to silica via ammonium

exhibits

high catalytic

spectra

the triruthenium

f79]. Various

cluster

or pyridinium

activity

framework

polystyrenes

than the tetraHRu3(CO)il,

functional

at lOO-150°C.

cluster

aminated

more active

triruthenium

anchored

150°C

H4Ru4(CO)8(PPh,C,H4-SIL),

at 15U°C. The mononuclear

complex

[78]. The anionic

to silica via phos-

groups,

According

remains

to 1R

intact up till

were examined

as supports

solvent at 80°c. for Rh6(CO)l6 used as catalyst in 2-ethoxyethanol The polymer prepared from chloromethylated polystyrene and diethylenetriamine

was

found to be the most

ions in seolite

form high valent

carbonyl

duced by

H20 + CO or H2 + CO mixtures

carbonyl

complexes.

into organic

These

substrates

show catalytic

activity

from Fe(C0)5 towards

and OH- hydrates

decarboxylation

that the anion must be deprotonated and conditions

in the gas phase and

for the condensation

of HN(CO)i

conditions

HOs(CO)q HOs3(CO)& 6.

Ru anion The

gas shift reaction

than

[831.

Reduction

with CO + H20

Polynuclear tively

does not form HFe3(CO)Il.

in the water

to

Under Water

/lOO°C and 1 bar CO/ the mononuclear

but HFe(CO)i

is more active

anion

by Fe(C0)5.

was studied. It was concluded losing CO2 [821. Stoibefore

HM3(c0)11

trimerizes

[Sl!.

is an important

catalyzed

gas

shift

metal

in CO insertion

for M = Fe, Ru and OS have been determined.

rapidly

metal

are re-

gas shift reaction

gas shift reaction

Its formation

which

and polynuclear

acid anion Fe(C0)4COOH-

of the water

its stability chiometries

[80]. Transition

complexes

to mono-

and in the water

The iron carboxylic intermediate

effective

reduced

aromatic

and heteroaxomatic

under water

compounds

gas shift conditions,

were

or with

selec-

synthesis

gas or H2 using Fe, Mn, Co, Rb, Ru, Cr. Mo or W carbonyls as catalysts.Polynuclear heteroatomic N compounds were more reactive and the heterocyclic carbonyl

ring was reduced

in the presence

regioselectively

[841. Iron penta-

of 820, CO, base and a phase-transfer

agent

349

catalyzes

the reduction

of nitrogen

in the nitrogen-containing reduced

ring at 150-300°C.

in the 9‘10 positions

cene yields products. chanism

nearly

Results

precursor.

throline

derivatives

Addition

yields

nuclear

Rh carbonyls as active

catalysts

a catalyst and methoxy

system

Hydroformylation

were

composed

are

transformed

at 80°C with

of Pt(PPh,),Cl2

Transformations

are formed

systems.

+ SnC14 +

were not affected

with a Co2(COj8

in a secondary

1871.

of CO and CO2

(70-280 bar, H2:CO = 2:l) yields

which

l,lO-phenan-

catalyst

in high yields

substituents

of olefins

as

at 165OC 30 bar CO. Mono-

[86]. Nitroarenes

MiscellaneousReductive

of formates

to active

by phen or its derivatives

aminoarenes

+ Et3N. Chloro

high pressures

as the me-

Rh6(CO)l6

of phen or substituted

substituted

CO + H20 using

7.

process

by CO + H20 with

of 100% may be achieved

into the corresponding

alSO

and trans-dihydro

transfer

leads, however,

Aniline

is

9,10-dimethylanthra-

[851.

is not reduced

catalyst

regarded

of the cis-

an electron

regiospecifically

Anthracene

by this system;

equal amounts suggest

of hydrogenation

Nitrobenzene

heterocycles

+ PR3 catalyst significant

reaction

at

amounts

from aldehydes,

CO and H2: RCHO+H2+C0 Highest having

yields

Synthesis effects gation

of formates

small cone angles,

(46%) were achieved

the hydrogenation,

with phosphines

[881.

of Co2(CO)6(PPh3)2

carbonylation

C

N

N-CH$ii3

C

-

precatalyst

and subsequent

to N-alkylpiperidines:

C

ate. -

RCH2COCH

like PEt3 or PM@3

gas in the presence

of pyridine

Referencesp.435

-

C

N-CHO

N-CH3

homolo-

350 Reaction

conditions

is also homologated and labeling

are 212OC and 80 bar. N-methylpiperidine

under these conditions

experiments

to the ethyl derivative

show that in this case the reaction

by the fission of the Me-N bond

starts

1891.

Carbon dioxide

is reduced to formaldehyde, formic acid and 2+ oxalic acid with reducing agents such as Cr , v2+ or Mo5+ in the presence

Tic13 -treated

to alkyl formates HM(C0);

zeolite CaA [go]. Carbon dioxide

in alcohol

(M = Cr, W) anionic

conditions

solutions carbonyl

is reduced

by H2 in the presence

hydrides

of the

under rather mild

(125OC, 30 bar CO2 + H2): CO2 + H2 + ROH

-

HCOOR + H20

Although

the water gas shift reaction also takes place under these conditions,experiments with 13 CO-labeled catalysts provide evidence against

the formation

Rh(dppe)2C1 solution. nitrile

catalyzes

from CO and ROH 1911. The complex

the electroreduction

The reduction

product

of CO2 in acetonitrile

is the formate anion, and aceto-

is the source of the H atom in the product

III. Hydrogenation 1,

of formates

formate

[92].

and Reduction

H-D Exchanz ---The H-D exchange

temperature reductive complex

between deuterobenzene and H7Re(PCy3)2 in the n range 60-80-C proceeds over H5Re(PCy3)2 formed by

elimination

of H2. Deuterium

not only as hydride

and C3 carbons catalyzes

of all cyclohexyl

the H-D exchange

PPr3. The reaction than benzene

rings

position

dissociation

of coordinative

aromatic

is slow with PCy3, and toluene

[94]. The complex

at the central methine

into the

[931. The complex

between deuterated

Rh[P(OPh)3]2(acac)

exchange with D2 at the ortho positions port complete

is incorporated

ligands but also selectively

H~R!J(PP~~)~

solvents

and

is less reactive (A) undergoes

of the phosphite

H-D

ligand and

of the acac ligand. The data sup-

of Hacac which generates

unsaturation

at the C2

at the Rh center.

a high degree

It is suggested

a complex of this type may be involved

in the hydrogenation

arenes catalyzed

of the type Pd(PR3)n

by (A)[95]. Complexes

Catalyze the H-D exchange reactions substrates, at ambient temperature.

between

D20 and various

The following

that

of (n = 3,4) organic

order of decreas-

351 inq rates has been found: RN02 Z+ RCN > R2CO Z+ RCOOR, nitroalkanes

deuteration

Copper(I)-coordination H-D exchange

on the terminal

RC=CH With

only at

+ CD3COOD

carbon

e

does not involve

Hydrogenation

a)

by a factor of 1.2~10~.

formation

hydrogenation

was investigated Turnover

Fe(CO)3(C2H4).

is a thousand

liquid-phase

The

[97].

of ethene with Fe(CO)4(C2H4)

in the gas phase.

hydrogenation

the laser isthermally

active,

of AlC13. With

= 3, and increased

Activity

of Fe(acac)3

1-hexene

or 1,3-pentadiene H2 pressure.

ation of the alkene

hydrogenation

to the Fe atom

and dppe in toluene,

NaBHa

is an active

in EtOH,

its of the homogeneous

involves

in or

as well

complexprepared

by a treatment

for the hydrogenation

of a -olefins

with of ole-

maximum

increasing

due to the formation

of dimeric

the activity

under mild cycle

remains

using

The rate passes throuqh a

concentration species.

is

conditions

[103]. The kine+

of cyclohexene

has been studied. catalyst

and cycloolefins

liqand probably

the catalytic

hydrogenation

as catalyst

Referencesp.435

catalysts

on the Al:Fe

of the catalysts

mechanism

l-20 bar). The arene

Ru(PPh3)3C12

Et3N increase

+ A1C13

‘_rl*-COD) complexes

to the Ru atom during

with

at

[lOOI.

ElOl]. The iron complex

catalyst

hydrogenation

by Ru( q6-arene)(

(room temperature, attached

rate was highest

11021.

Homoqeneous catalyzed

in

depended

followed

by

as catalyst

(lo-100 bar)

of preparation

The reaction

from Fe(acac)3 fins and dienes

reaction

+ SnC12 and Fe(acac)3

Sn:Fe ratio and the method the

l-hexene

generated

[991. Unsaturated

with Fe(acac)3

with H2 pressure

species

for the fastest

[98]. The catalyst

not photochemically

the presence

as

is -1 was found to be 900 s

than that known

system

could be hydrogenated

on

The active

rate of the process

times larger

hydrocarbons

as

+ CD3COOH

of Olefins

Photocatalytic

Al/Fe

[961.

the rate of

atom with CD3COOD:

RsCD

alkynide

position

increases

Fe and Ru Catalysts

catalyst which

the Cl

alkynes

1,7-octadiyne the rate increases

exchange

2.

occurs

to terminal

RX, ROR.. For

which

is probably

Low concentrations

of the system but at higher

of

concentra-

352 tions the rate decreases hydrogenation

with 100% selectivity complexes

[1041. The Ru complexes

of cyclohexene

(21) catalyze

and high turnover numbers. Analogous

which do not contain a cyclopentadienyl

to be less selective

the

and of the C-C bond of norbornenone Ru

ligand were found

ilO51.

n = 3,4

The reaction of RuCl2. 3H20 and a carboxylate sized from a chloromethylated treatment

of the supported

the formation bridging

(syntheand

complex with sodium acetate results

of a polymer-supported

ruthenium

is probably analogous

is

complex containing

acetate groups and showing only minimal

in DMI?. Its structure +

polymer

resin) in acetic acid/ethanol

Ru elution at 85OC

to that of

[RU~O(OAC)~(H~O)~~ . The activity of this supported complex as

olefin hydrogenation See also

b)

catalyst has been studied

[1061.

15881. Co,

Rh and Ir Catalysts

The effect of varying concentrations NaOH, mono-,

di-, and trialkylamines

of Co(dmg)2

on the kinetics

catalyst, of the homoge-

neous hydrogenation

of fumaric and maleic acids was studied. Di-

alkylamines

the most active catalysts

yielded

of co12 + MgBu2,

Co(acac)2

+ MgBu2, Co(acac)2

MgBuI, and C~(acac)~

+ MgBu2 catalysts

various

individually

hydrocarbons

CO12 + MgBu2 genation

in the hydrogenation

>> cyclohexene

have been used as catalysts

of

naphtalene

[lOBI.

and

11081. The complexes

MeCo(CO)3P(OMe)3

and PhCH2Co(C0)3PP%

for the hydrogenation

of 1-alkenes.

Each was active but their lifetime was much shorter than that of MeCo(C0)2[P(OMe)312

+

the rate of hydro-

> anthracene-

is first order in cyclohexene

MeCo(CO)2[(MeO)2PC2H4P(OMe)21,

Co(acac)3

depends on the Co/Mg ratio. Using

in THF at 25O and normal pressure

is norbornene

the reaction

[1071. The activity + MgBuBr,

353

Hydrogenation

of atropic acid and its esters with ~[Hco(cN)~]

in a water solution containing

5% 1,2-dichloroethane

ed by the neutral surfactant polyoxyethylene This effect is attributable and the catalyst

to

23 dodecyl ether.

concentration

in the micelles

is accelerat-

of the substra.te

[IlO]. A nonionic

surfactant Brij

35 was also useful to promote the [Co(CN)5]3--catalyzed tion of styrene in micellar dimethyl(

hydrogena-

solution. However, the use of dodecyl-

CL-methylbenzyl)-armnonium bromide as a phase-transfer

agent resulted

in more efficient acceleration

of the reaction rate

[llll. Deuteration Rh(PPh3)3C1

of p - acyloxy crotonates

is a 2~

There is no regioselectivity,

Me\

(22) catalyzed by

process with very high stereoselectivity. however,

C = CHCOOMe

in the addition of HD [112].

22

(Z

and

E)

PhCOO’ By systematic variation of the phosphine phine complexes

ligand in Rh phos-

the catalytic activity in olefin hydrogenation

has

been enhanced by a factor of > lo4 relative to the activity of Rh(PPh3)jC1.The following modifications

were examined: varying the

basicity of the ligands, replacing Cl- by the non-coordinating use of a chelating diphosphine,and diphosphine

BF;,

varying the chain length of the

[113]. The influence of the number, position and struc-

ture of OR-substituents

on the phenyl rings of tertiary aryl phos-

phines upon the rate of hydrogenation phine complexes

as catalysts was investigated.

within three orders of magnitude, obtained with

of 1-hexene using Rh(I)-phos-

(23) as a ligand. Triarylarsines

activity catalysts

Initial rates varied

the most active catalyst was

than the corresponding

gave generally

triarylphosphines

lower

[1141.

OPri Ph2P

/

0 iPr0 The activity of Rh(PPh3)3X neous catalysts

23

\

(X = Cl, Br, I) complexes as homoge-

for the hydrogenation

Me esters decreased

in the order

of cyclopropene

I>Br>Cl.

complex was found, however, to be too susceptible practical use [115]. RhL(CO)2C1

Referencesp. 435

to oxidation

and RhL(CO)(PPh3)C1

cumarin) complexes prepared from Rh2(CO)qCl2

fatty acid

The most active iodo for

(L = 3-amino-

or Rh(C0)2(PPh3)Cl,

364 respectively, cyclic

and L, catalyze

olefins

H2 to yield species

ter complex

-H) RhH(L-L)]C104, 53 -Fe( lj -C5H4PPhBut)2].

are catalytic

for olefin

and

reacts with

a trihydride-bridged Solutions

hydrogenation

of the type Rh(CO)(L)(acac)

lysts for the hydrogenation

of linear

[(L-L)R~(NBD)]C~O~

[(L-L)HRh(p

[(L-L) =

complexes

the hydrogenation

[116]. The complex

of this lat[117]. Rh(I)

(L = 24) were used as cata-

of 1-heptene

at 70°C and 1 bar

[118].

00

R2N-P

‘0

R2N= m2N, Et2N,

24 Homogeneous

hydrogenation

lenecyclohexanemethanol catalyst

afforded

practically alcohol tivity

(25) with

equal amounts.

The structurally

of the OH group

(28b). These results

CH3

CH2OH

CH20H

CH2

[1191.

26 b

47%

CH3

-Q OH

27

8H < 2%

28 a

Hydrogenation The results

the coor-

+

CH3

OH

bis

98% selec-

suggest

+

several

as

(26b) in

hydrogenation

53%

26 a

2-methy-

homoallylic

with over

to the Rh atom during

CH2

25

(26a) and similar

could be hydrogenated

to the trans alcohol

alcohol

[Rh(Ph2PCH2CH2CH2PPh2)(NBD)jBF4

the cis and trans alcohols

(27), however,

dination

of the homoallylic

28 b

of 3-methyl-3-phenyl-1-butene

was

’ 90%

studied with

(triphenylphosphine)rhodacarborane

catalyst

prove

does not participate

in the catalytic

that the icosahedral

has a (phosphine)(alkene)Rh(I) rhodacarborane

clusters

the hydrogenation

cluster

cycle and that the operational exo-nido

(29) and

precursors.

catalytic

structure

species

[1201. The two

(30) were used as catalysts

of 1-butylacrylate

. A catalytic

for

cycle was pro-

355 posed

that involves

culminates

exo-nido-rhodacarboranes as intermediates and -in the elimination of l-butylpropionate from such a

reversibly

formed

intermediate

(31) [121].

30

29

Hydrogenation as catalyst had a strong with maleic nounced

of unsaturated

in water

involving

complexes

was observed.

cationic

-CH=CH2),

dienes

(e.g. PhCH=CHCHO)

OL , p -Unsaturated

as catalyst.

of olefins and

carbonyl

procata-

complexes

as

(e.g. p-MeOC5H4

a, p -unsaturated

was carried

car-

out using Rh2(BD)2C12

compounds

of the C=C bond. The active

tive hydrogenation

acid whereas

phosphinerhodium

carboxylate

hydrogenation

phosphine

three parallel

Rh complexes,

(e.g. 1,4-octadiene),

compounds

Excess

Rh(tpm)3C1

These unusually

by assuming

and phosphinerhodium

[122]. Biphasic

acids with

in the case of crotonic

were explained

catalysts bony1

carboxylic

has been studied.

effect

acid no inhibition

differences

chloride

solution

inhibiting

lytic pathways

31

underwent

catalyst

selec-

is colloidal

Rh [123]. The activity

of the catalyst

systems

formed __ in -situ from (R = H, Me, OMe) for the hydrogena-

Rh2(I'JBD)2C12 and (P-RC~H~)~P tion of 1-hexene changes on ageing tion in the presence responsible which

for this phenomenon:

decreases

The cationic the similar of the Rh(1)

Rh(1)

as catalyst complexes cation

Referencesp.435

catalyst complex

the oxidation

to sulfonated

solu-

to be

of the phosphine degradation

which

[124]. [Rh(NBD)(dppe)](TsO)

for the hydrogenation

containing

precursor

are regarded

the P/Rh ratio and a successive

leads to an unidentified as effective

of the catalyst

of air. Two processes

proved

of soybean

ClO, or PF; counterions. polystyrene,

however,

to be

oil as Binding

resulted

356 in a total

The activity genation

treated with LiPPh2

of the catalyst

of cyclohexene

supported genation

11251. Polyethylene

lack of activity

were brominated,

on a polystyrene

L = HN(CH2CH2PPh2)2] with H2MLC1

species

as catalyst

data suggest

alcohols

increases

[Rh(NBD) (Ph2PCH2CH2CH2CH2PPh21]El?4

catalytic

hydro-

[M = Rh, Ir; a mechanism

[127]. The diastereoselectiv-

some acylic olefinic

than the II? complex

MLCl

Kinetic

of cyclic olefinic

With

than that of Rh(PPh3)3Cl

[126]. The homogeneous

as intermediates

[Ir(COD)(PCy3)py]PF6

selectivity

in this way was for hydrohigher

with the complexes

was reported.

ity of hydrogenation concentration.

obtained

significantly

of cyclohexene

single crystals

and then with Rh(PPh3)3Cl.

like

(32) with

with decreasing

alcohols

exhibits

catalyst

the complex

even better

diastereo-

[128, 1291.

OH

OH

32 See also

[33, 1341

c) Ni, Pd and Pt Catalysts Mixed

organometallic

catalysts

(M = Cr, Fe, Co, Cu) and AlEt tion of sunflower obtained

selectivities and acrolein ligands

oil than the analogous

from Ni(st)2

The effects

and Et3A1

obtained were

as catalysts.

a catalyst chored

Hydrogenation

After

for olefin

genate more

of monoalkenes. easily

that the reaction

with N-containing was 100% selective and 2,4-toluene

[132]. Palladium

Terminal

from

the complex was used as acetate

has been used as catalyst

than internal proceeds

of 3-(2-furyl)acrolein

diacetate

with LiA1H4

hydrogenation

on the

complex was prepared

palladium

reduction

catalysts

additives

of'&rolein

cl31]. A polymerPd

to polystyrylbipyridine

hydrogenation

solvent,and

using Pd complexes

4,4-diamino-2,2' -bipyridine

+ M(st),

for the hydrogena-

single-metal

in the hydrogenation

studied

of Ni(st)2

[130].

of temperature,

for C=C reduction diisocyanate.

composed

are more active

olefins

ones. Kinetic

via two parallel

an-

for the

were found to hydroresults

mechanisms

indicate [133]. The

357 2olefin isomerization catalyst obtained from [PtC12(SnC13)21 , 43[RuC1(SnC13)5] supported on an anion ex, or [RhC14(SnC13)21 change resin (AV-17-8) are turned into olefin hydrogenation catalysts by addition of K2ReOC15

[134].

See also C2021 d) Other Metals Photolysis of 1-alkene results

-RlYn(C0)4PPh3 in the presence of H2 and

in catalytic hydrogenation

and isomerization

of

the alkene. The catalytic cycle can also be entered by use of cis-MeMn(CO)4PPh3. of the reaction

(Alkyl)Mn(CO)4PPh3

complexes are intermediates

[135].

Alumina-silica

possessing various A1203/Si02

ratios was reac-

ted with CpTiC13 and the resulting Ti complexes on the surface reduced by an excess of BuLi. The supported Ti complexes were tested as catalysts

for olefin hydrogenation.

Active catalysts contain-

ed large amounts of Ti(II1) and the most active Ti(II1) complexes were supported on alumina-silica The polynuclear lyses the homogeneous

3. Asymmetric

having

thorium hydride hydrogenation

Hydrogenation

~50%

A1203

[136].

[Me2Si(Me4C5)2ThH2]x of hexenes

cata-

[137].

of Olefins

Interest in the preparation

of new chiral ditertiary

phos-

phines is diminishing.

More emphasis was put on the synthesis of

chiral aminophosphines

or phosphinites

containing

additional

interactions

heteroatoms

and also of phosphines

in the side chain which enhance

between the ligands and the substrate.

The enantiomers

of the chiral diphosphines

(33) and (34)

(R i= CH2PPh2) were prepared and used as ligands in the asymmetric hydrogenation

of unsaturated

carboxylic

between 10 and 82% were obtained

33

Referencesp.435

acids. Optical yields

[1381.

34

358

The modified

DIOPs

(35) and

for the asymmetric

hydrogenation

dehydrodipeptides.

Best results

modification

at the dioxolane

on enantioselectivity

(36) were prepared of

were obtained

ring

(ligands

with

acid and

(36d), the

35) had little effect

[1391.

0

PPh2

H i

PPh2

Me&

PPh2

‘0 xl

H

PAr2 H

35a,

Ar

=

2-naphthyl

36a,

Ar=

35b,

Ar

=

1-pyrenyl

36b, 36c,

Ar=p-methoxyFh=yl Ar = 1-naphthyl

36d,

Ar

N,N-bis(diphenylphosphinomethyl)amino chiral

ligands

cinnamic Optical

in the asymmetric

yields

of about

acid used

These

relatively

6-membered lytically because

active

were

ring formed

complex

tartaric

phosphine

was achieved :catalyst

explained

The preparation complexes

starting

from natural hydrogenatioh

acid with Rh complexes.

(R)- and

yield

(50 bar) and high substrate

37

of both enantiomers (S)-BINAP

tion of 2-(acylamino)acrylic [142].

99% optical

[1411.

bis(triaryl)phosphine of

11401. The chiral

in the asymmetric

NCOPh

isomeric

that the

in the cata-

chair conformation

C atom

(37) has been prepared

(1OOOO:l)

bisphosphine.

by the fact

may have a nonchiral

even at high pressure

ratio

a-acetamido-

in situ catalysts. -independently of the

by Rh and the ligand

acid and used as a ligand

a-acetamidocinnamic

of

of the chiral

of the 4-position, of the chiral

ditertiary

2-na#khyl

acids were used as

30% were achieved

low values

=

+ phosphine

for the preparation

chelate

p-tolY1

hydrogenation

acids with Rh2(diene)2C14

amino

of

and applied

a-acetamidocinnamic

of BINAP

has been described catalyze

acids with

(38), an atropin detail.

the asymmetric 67-100%

optical

Rh(I)

hydrogenayield

359

38 PPh2

Asymmetric dehydro chiral on

hydrogenation

phenylalanine diphosphines

was

was

of(.o-heteroarylwas

investigated.

one

heteroatom

a five-membered

The

ring

Rh(1)

effect

Substrates

were

with

more

two

containing

heteroatoms

with structure

Asymmetric acids

reactive

containing

complexes

of peptide

[143].

a-acylamido)acrylic

ring

cycle

oligopeptides

using

investigated

complexes with

several

as catalysts.

enantioselectivity

nation

of

performed

hydroge-

with

Rh(I)-DIOP

a five-membered

than

those

containing

or a six-membered

hetero-

[1441. A number

(39-41)

have

asymmetric acids.

of been

isomerically tested

hydrogenation

Highest

related

as ligands of

chiral

bis-aminophosphines

for rhodium

catalysts

cl -acetamido-cinnamic

enantioselectivities

were

obtained

in the

and

-acrylic

with

ligand

(41)

[1451.

0

CH2-YR

Y

PPh2

PPh2 The were of

axially

prepared

and

dissymmetric used

d -acylamidoacrylic

were

obtained

39,

R

=

(S)-(-)-PhMsCH-

40,

R

=

(R)-(+)-PhMeCH-

41,

R

=

diphosphine

in Rh(I)-catalyzed acids

and

esters.

PhCH2

ligands

Optical

Ye NPPh2

NHPPh2

42

TPPh2 MQ 43

(43)

hydrogenation

yields

11461.

NHPPh2

Referencesp. 435

(42) and

asymmetric

up to

95%

360

Several

chiral

from optically N-methyl

aminosphosphine-phosphinites

active

amino alcohols

The new ligands were tested

phenylglycinol.

hydrogenation The ligand 70-80%,

of d -acetamidoacrylic

(44) prepared

the others

were

were prepared

like ephedrines,

and

in asymmetric

acid with Rh(1) complexes.

from prolinol significantly

afforded

optical

yields

less enantioselective

c-5

CH20PPh2

N

prolinol

of

[147].

44

bPhp formed -in situ from Rh(COD)2C12 and the optically S_PhCH2CH(NPPh2Me)CH2OPPh2, (1R,2SkPhCH(OPPh2)

Complexes active

ligands

or @R,2R)-PhCH(OPPh2)CHMeNPPh2Me

CHMeNPPh2Me

of PhCH=C(NHAc)COOH yield

[148]. The Rh(1) complexes

(45) act as efficient hydrogenation above

of

asymmetric

prepared

phosphinite

alkenes

Optical

homogeneous

catalysts acids.

for the

Optical

yields

[149].

(46), a derivative

and used as ligand

prochiral

hydrogenation

in 2-4%

of the new chiral phosphinite

(Z)- ci-acylamidocinnWc

90% were achieved

The chiral

catalyzed

to give @+PhCH2CH(NH.Ac)COOH

in the asymmetric

with Rh(1) catalysts

of L-rhamnose hydrogenation

was of

[1501.

46

Seven different

chiral

diphosphinites

of the type

used in the form of Rh(1)

complexes

for the asymmetric

tion of dehydrodipeptides

[151], dehydroamino

(47) were hydrogena-

acids and itaconic

acid [1521. Extremely high diastereoselectivities (> 98%) due to double asymmetric induction were observed in hydrogenating dehydrodipeptides

with

ligands

containing

an

w -dimethylaminoalkyl

group.

361 Alc=Ph

Ar2PO NR ‘c AqPO*“”

R=

?!CV@@2

-CsH4

M2CH2"Me2

-SH4 ph

cH2QI2"Me2 cH2cHzcH2=2

Fh 47

Asymmetric

hydrogenation

was investigated and the chiral

of

with catalysts P,N-ligands

lysts was rather respectively

cH2cH2-2

-SH4 Ph

cH2cH2-2 QI2p"

(Z)- aformed

acetamidocinnamic in situ from

(49) or (50). The activity

low and the optical

yields

??

5H lH N-c---Me 49

50

18 new optically as ligands

active

phosphines

configuration

appreciable

of the product

ing the P:Rh ratio

of the types

for the homogeneous

tion of N-acyl- a-aminocinnamic (53) showed

,H

l&H-C --- IbIg ‘Ph

Ph2P

‘Ph

Only

of the cata-

were only 17 and 14%.

[153].

Ph2P

were tested

acid

[Ph(COD)C112

acids at p:Ph ratios

asymmetric

(51) and

Rh-catalyzed

induction

formed occurred

(52)

hydrogena-

1.1 and 2.2.

(68). A change

of

in some cases by vary-

[154].

PRR’ c”~/NM=2 \R ” NMe2

Ph complexes near the N atom,

References p.435

containing e.g.

chelate

ligands

with asymmetry

(54), were used in the hydrogenation

centers of

362 a-acetamidocinnamic

acid. The low optical

suggest that the catalyst to racemization

inductions

loses its chirality

or fragmentation

obtained

during catalysis

due

[1551.

54

Ph Fixed chiral Rh(1) complexes by treatment

and the chiral phosphine, hydrogenation retained

of DIOP or BPPM

of charcoal with metal acetates

were used as catalysts

of Cc-acetamidocinnamic

its activity

(55), prepared

followed by Ph2C12((ED)2 for the asymmetric

acid. The recovered

catalyst

[1561.

pph2

h-

55

CH2PPh2

BPPM

Y COOBut

The catalyst asymmetric

system CoC12/(+)-nmenPh2P/NaBH4

hydrogenation

of PhCH=C(NHAc)COOMe

afforded

to (S)-(+)-PhCH2CH

(NHAc)COOMe optical yields of < 60%. The catalyst leucine)2Co/PPh3/NaBH4 -carbon

as cocatalysts cal yield

hydrogenation

+ achiral base catalyst

(79%) was achieved

(56) 'as chiral ligand

and used

of (58) and (59)

in the hydrogenation

of (59) using

OAc

Ph

56

[157].

system. The highest opti-

[158].

MqN

(L-iso-

amide group at the

(like (56) and (57)lhave been prepared

in the asymmetric

with the Co(dmg)2

system

gave a much lower o.y., however

Several chiral tertiary amines with a secondary a-orp

in the

/H CONHC, \-Ma H 57

363 PhCH = C -N,M”

,COOMe CHp=C

I OC -

‘NHAc

59

58 Ethyl

a -methylcrotonate

or NiC12[(-)-DIOP] of Et3N increased remained

Jo NMe

was hydrogenated

as catalyst

at 80-100°C

the conversion,

still rather

with CoCl2[(-)-DIOP]

and 50 bar. Addition

but the activity

low. Optical

of the catalysts

yields of l-12% were achieved

L1591.

4.

Hydroqenation

of Dienes

and Alkynes

a) Fe, Ru and OS catalysts During hydrogenation f AlEt

catalyst

of alkynes

the amount of which changes The catalytic pyridine)

activity

polynuclear

parallel

of a MoFeS

in the hydrogenation

the catalyst MeCN

and alkenes using the Fe(st)3+

system an associated

with a solution

complex

with catalytic

complex

supported

of acetylene

obtained

[160].

on poly(vinyl-

is increased

by mixing

is formed

activity

by treating

FeC12 and NaHS in

[161].

Ru2Fe(CO)12, RuFe2(CO)12 and Fe3(C0)12 all catalyze Ru3;CO&, the hydrogenation of pentynes and pentadienes at 80°C and 1 bar both in toluene complexes on

solution

decreases

y-Al203

ana anchored

with increasing

leads to decrease

but increases

activity

to y -A1203. Activity

of the

number of iron atoms. Anchorage

in activity

for pentadiene

for pentyne

hydrogenation

hydrogenation

[162].

catalyzes the .homogeneous hydrogenation of Ru( 7' -COD)( +C8Hlo) 1,3- and 1,5-COD to cyclooctene at room temperature and 1 atm H2 in THF or alcohol hydrogenation Ru(PPh3)3C12

as homogeneous

high selectivity Rh(PPh3j3c1 minimal,

solvents.

1,5-COD

[163]. Hydrogenation under mild

the formation

but selectivity

isomerizes

to 1,3-COD before

of Me linoleate

catalyst

provided

conditions. of isolated

for monoene

using

a-monoenes

With H2RuiPPh3)4

with or

trans C=C bonds was also

formation

was somewhat

lower

[164]. H3CpNiOs3(CO) in solution

catalyzes

the hydrogenation

at 120 % C and 0.9 bar H2. When

Referencesp.435

of 1,3-pentadiene

supported

onto Chromosorb

364 P the activity

of the complex

both homogeneous See also

depends

and heterogeneous

upon pretreatment.

catalysis

Probably

11651.

occur

[171, 2641.

b) Co and Hh Catalysts Several

diolefinic

a -phellandrene, menthenes

in good yields

as catalysts asymmetric failed

at 70-100°C

hydrogenation

[1661. Binding

provides

a stable

hydrogenation dient.

nation

Co(CN)3(bpy)H-

as ligands

to monoenes.

as catalyst

of 1,5-COD resins

ratios

prepared

are

at

hydrogenated

In the presence

to

of bpy hydroge-

to the formation

of

derivatives

(60)

gave the decahydronaphthalenone [1691.

has been studied

loaded with

The yield of cyclooctene

Rhodium

ingre-

61

from Merrifield

but the yield requires

did not depend

chloride

catalyzed

prepared

and Hh2(CO)2C12.

on the P/Hh ratio of the was strongly

This suggests

the presence

of polyethylenimine

over catalysts

PPh2 groups

of cyclooctane

the P/F& parameter.

and ruthenium

solution

resins

[1671. Acetylenes

of the hexahydronaphthalenone

(61) in good yield

Hydrogenation

increasing

is a necessary

and partly

is attributed

exchange

in the three-phase

by cyanocobaltate nitriles,

60

cyclooctane

Water

anion

[1681.

with Hh(PPh3)3C1

catalysts

useful

neutral

hydrocarbons. which

phosphines

to various

catalyst

hydrocyanated

Hydrogenation derivatives

or HCO(CO)~(PBU~)~

by using chiral

to give secondary

or saturated

CL -terpinene, 3 1 A - and A to perform

is practically

predominates

to

and 20-30 bar H2. Attempts

of HCo(CN)z-

of dienes

regioselectively CN:Co <5:1

(like limonene,

with CO~(CO)~(PBU~)~

supported

The catalyst

alkenes

terpenes

etc.) have been hydrogenated

of vicinal

complexes

decreased

by

that the formation active

prepared

sites

[1701.

by mixing

the

and the salt in 2:l and 4:l N:metal

the hydrogenation

of cis- and trans-CH2B

of

365 to -trans- MeCH=CHEt under 5 bar of hydrogen pressure in the cis-2-pentene and pentana presence of NaBH4. Byproducts were l- and _.

mainly

[1711. See also

[164, 178, 2461.

c) Pd Catalysts A new, very ylenes

to (Z)-olefins

t-pentyl

alcohol

catalysts

of sorbate, olefin

and reduced

by

The product on minerai

of the reaction supports

of dienes

active

to olefins

was active

of conjugated

and propargyl

zeolite,

for the

with a selec-

and sulfide dienes

ligands

to olefins

lanthanide

for selective chloride

in the hydrogenation for benzene,

alcohol

ligand

catalysts

of PdC12 and trialkylamines

catalyst

but inactive

amine

to olefins

amine

of

Pd/C. Conju-

[1741. O2 and H20 activate

primary

[176]. Palladium

as a catalyst

CH2=CHCH20H

Pd complex

than unconjugated

a primary

or BuLi are active

(Y-A1203,

(did

Selectivity

than with

reactive

hydrocarbons

containing

hydrogenation

to be a highly

more

at 95% conversion

NaH, and

in the hydrogenation

linoleate.

Pd(acac)2

containing

(Me2CHCH2)2A1H of acetylenic

the selective

octanal,

with

was significantly

catalysts

[172]. Homogeneous

and conjugated

was higher

of 98-99%

from Pd(OAc)2,

of acet-

was self-terminating

Pd/C catalysts

[1731. Pd complexes

hydrogenation tivity

with

Me linoleate

linoleate

complex

to alkanes)

compared

formation

linoleate

for the hydrogenation

has been prepared

alkenes

were

catalyst

in THF. The catalyst

not hydrogenate

gated

selective

Pd in

[1751.

deposited

oxides)

proved

(> 94%) hydrogenation on the polymer of alkynes

naphthalene,

(62)

and

cyclohexanone,

[177].

62

Polyethylenimine

complexes

(CH2CH2NR),.MC12

(R = H, AC;

n = 150-200;

M = Pd, Rh, Co, Ni) catalyze the partial hydrogenation of cycloalkadienes and -polyenes to the corresponding cycloalkenes at 20-50°C and 1-5 bar. For example, 1,3- and 1,5-cyclooctadiene and cyclooctatetraene

Referencesp.435

were converted

to cyclooctene

with

90-94%

selectivity.

Catalytic

activity

decreased

in the stated order of

M [1781. See also

[2641.

d) Other Metals A polymer-supported

hydrogenation

catalyst,

@CH2(C6H40)

copolymer, R = H, Me, = sty rene-divinylbenzene (Cp)2TiOC6H4R, @ tBu) containing ~6% Ti was prepared and used for the hydrogenation of cyclopentadiene See also

1179, 1801.

1161, 165, 178, 2641

5. Hydrogenation-_-of Arenes Anthracene by H-transfer as catalyst. reaction.

and Heterocyclic

is hydrogenated

Compounds

to 1,2,3,4_tetrahydroanthracene

from iPrOH at 75OC with H4Ru(PPh3)3 1,2_dihydroanthracene

PPh3 and even N2 decrease

is an

or H2Ru(PPh3)4

intermediate

the activity

of the

of the catalyst

L1811. Selective compounds

hydrogenation

of the polynuclear

(63)-(68) could be achieved

(8S°C, 21 bar) with Rh(PPh3)3C1 tion of the ring containing

heteroaromatic

under mild conditions

as catalyst.

the heteroatom

In all cases satura-

was observed

63

64

65

66

67

68

[1821.

367

aromatic

Unsaturated, 1,4-benzodioxane,

and heterocyclic

1-hexene,

compounds

1,5-cyclooctadiene,

like furan,

and PhR

(R = H,

NO2, NH2, OH) were successfully hydrogenated on catalysts composed of Pt, Pd, Ni, or Rh complexed with styrene-maleic acid or methyl methacrylate-maleic complex

catalyst

acid copolymer

was prepared

or polyacrylic

by the reaction

poly (y-diphenylphosphinopropylsiloxane) The catalytic aromatic

6.

activity

compounds

Hydrogenation

of the complex

was greatly

of Carbonyl

The electrochemical the presence

of Fe(I1)

as catalyst rather

precursor

creasing already ortho

unreactive

isomer

phthalide PhCOCF3

and methyl

in transfer

mediates

of the catalytic

genation

of unsymmetrically

to achieve dimethyl

with

in-

glutarate

acid Me esters

is

only the gives

[186]. Hydrogenation with

of

The Ru complex

iPrOH or EtOH as

Ru and Rh alcoholates

which

have been prepared

substituted

is

significant

decreases

and HRh(PPh3)4.

hydrogenation

with mono-,

the isomeric

the bulkiness phosphine

bar. The reaction

This latter compound

as products

reaction

in DMF in

cyclic

are inter-

[1871. Hydro-

anhidrides

(69)

Ph, R1 = H, n = 1; R = Me, R1 = H, Me, n = 1,2) catal-

yzed by Ru complexes produced

the phthalic

by H2Ru(PPh314

ketones

esters with Ii4Ru4(CO)8(PHu3)4

of the substrates

benzoate

[184].

[1851. Esters of dicarbox-

days are required

The corresponding

(R = CHMe2,

of aromatic

to hydroxy

and among

ratio

acid. of

Compounds

could be hydrogenated.

is also active

by the P/W

of the two ester groups,

is catalyzed

H-donors.

affected

reduction

The reactivity

distance

with chloroplatinic

at 180°C and loo-150

slow and several

conversions.

[183]. A Pt

in the hydrogenation

salts was studied

ylic acids are hydrogenated

acid

of silica-supported

lactones.

di-, or triphosphine Regioselectivity

of the substituent(s)

ligands

of the catalyst

was

on the anhydrides

ligands influenced and on the

[188].

69

0 Catalytic

analogs

of LiA1H4,

(701, K2[(Ph3P),(Ph2P)Ru2H41r

References p. 435

the hydridophosphineruthenates

and K[(Ph3P)3RuH312-,

prepared

by

by

reduction

of Ru phosphine

hydrogenation aldehydes, hydride

catalysts

nitriles,

catalysts

of the type

to their anionic nature

method was developed

of such polar double [190].

for the transformation

groups of chiral diphosphines

(71) have been prepared

a-hydroxy

like ketones,

[189]. The ability of these new Ru

dicyclohexylphosphinoyl

in the asymmetric to

for polar organic compounds

and esters

the diphenylphosphinoyl corresponding

are very active homogeneous

to promote hydrogenation

bonds is attributed

A new preparative

complexes

hydrogenation

into the

groups. Chiral diphosphines in this way and used as ligands

of o(-dicarbonyl

compounds

carbonyl compounds with Rh(1) catalysts.

yields were moderate

of

(72,73)

Optical

[191].

P /O Ph-C-CNNHCH2Ph

CYPCY~ ~ONHR 72

71

73

The same method was used for the preparation analogues

(74,751 of 6&DIOP

chiral diphosphines

and

of the cyclohexyl

(S,S)-Chiraphos.

and (731, giving somewhat higher optical yields than

v

I0 ’ Me2C, 0 xl H

Me

PCY2

Kinetic

investigation

PCY2

of the hydrogenation

conditions

increases with increasing

(71) 11921.

PCy2

75

of a Rh complex-tertiary

hydroformylation

of (72)

H

Me 1 i H

PCY2

74

the presence

These new

were also tested for the hydrogenation

of aldehydes

amine catalyst

in

system, under

showed that the optimum CO pressure

concentration

of amine. This was attri-

369

buted

to a competitive

lytically

active

also

7.

coordination

Rh complex

of CO and amine on the Cata-

[19X1.

[2021.

Hydrogenation

of Nitro Compounds

Complexes Of Re(V) with thiourea, N,N-ethylenethiourea, 2-benzimidazolethiol, and 1-methylimidazole-2-thiol are soluble catalysts

for the hydrogenation

stability

increases

Reduction -transfer amount

in the stated

of nitrobenzene

conditions

of Co2(CO)8

as catalysts binuclear

complex

Their activity order

however,

NaOH and a catalytic

in the reduction

The complexes

The

catalyst

catalyzed

in

hydrogenation

as the first detectable

trans-Pd(py)2X2

of nitroaromatics

inter-

olefins

and aliphatic

The chloro

complex

is the most

PhN02 by hydrogen

(X = Cl, Br, I) catalyze

at 30°C even under

Aldehydes,

nitro compounds

active

in the presence

phosphonate

or rhodium

and acetylenic

complexes

groups

for hydrogenation nitro compounds

ported

poly(vinylpyrrolidone)-Pd

complex

and atmospheric

The catalyst

pressure.

by the addition

catalyst

was prepared

nethylated catalyst

polystyrene can be used

at 60-90°C

handled

in air

copolymerized polymer prepared

of equimolar

by attaching

bar.

in the presence with

of propene sup-

at room tempewas in-

[200]. A polymer-bound

Pd

acid to chloro-

the polymer

with

PdC12.

of aromatic

The

nitro com-

It has a long lifetime acid and divinylbenzene

and may be were

of Si02 and the silica-supported

PdC12 or H2PtC16.

in this way catalyzed

Referencesp.435

of nitro-,

stability

anthranilic

and treating

[201]. Methacrylic

treated

HOAc

[1981.

Zr(IV)-

by a silica

was studied

for the hydrogenation

and 30-100

on layered

or for the hydroformylation

of aromatic

of

or PdL'Cl

was studied

supported

rature creased

are not reduced.

HL' = l-(2-pyridylazo)-2-naphtkwl

were used as catalyst

[199]. Hydrogenation

the

pressure.

[197]. The hydrogenation

or 1-(1-(2-hydroxynaphthyl)azo)-4-sulfobenzene] Palladium

normal

of NaBH4 and Na(PdLC1)

[H2L = 4-(2-pyridylazo)resorcinol,

pounds

compounds

to aniline.

may be the active

[195]. The cobaloxime azoxybenzene

phase

[196].

hydrogenation

cyano-

under

The use of both metal

CO(CO)~R~(CO)~C~-

gives

and

[1941.

not be performed

with CO in benzenej5M

process

of nitrobenzene mediate

ligand

could

or Rh2(HD)2C12.

resulted,

the reduction

of PhN02.

The Pd and Pt complexes

the hydrogenation

of nitro compounds,

370 alkenes, 8.

aldehydes, and ketones

Miscellaneous

Hydrogenations

N-Benzylideneaniline Fe(C0)5

as catalyst

The HFe(CO)g

[2021.

is hydrogenated

in alcohol

to N-benzylamine

anion is regarded as the catalytically

In a stoichiometric

reaction

rapidly at room temperature from [Rh(NHD)C112

H2Fe(C0)4

hydrogenates

active

the Schiff base

prepared -in situ of the type Ph2KHRCH2PPh2

and chiral diphosphines

of the Schiff base PhMeC=NCH2Ph,

ibility of the results was poor reduction

of pyridinium

1,4_dihydropyridines of a substituted

species.

[203]. Using catalysts

(R = Ph, iPr, PhCH2) optical yields above 60% were achieved hydrogenation

with

solution at 150°C and 100 bar H2.

but the reproduc-

[2041. Catalytic

or stoichicmetric

salts (76) by Co(I) complexes

of Hdmg gave

(77) with high regioselectivity.

tetrahydrobipyridine

suggested

pyridyl cobalt complex was the reactive

in the

The isolation

that a dihydro-

intermediate

[205].

CONH2 77 R

N,N-Dial)@ methylamines

can be hydrogenated

using homogeneous

group 8 metal precursors

formamides

catalysts

R2NCH0 + 2 H2 is rather sluggish,

100 moles product/moles

9.

derived

from a variety of

(Ru, OS, Rh, Ir and Fe) carbonyl cluster catalyst

at 220°C and about 100 bar

The reaction

to the corresponding

Coordination

-

(H2:C0 = 16:l): R2NCH3 + H20

turnover numbers do not exceed

catalyst day [2061.

Chemistry

Related to Hydrogenation

Reaction of Ru3(CO)12 with PhCN and H2 at 130°C yields a complex of PhCH=NH, which is a partially of PhCN. Further These reactions benzonitrile

treatment

derivative

of this complex with H2 results

model some possible

on a metal

hydrogenated

surface

(781, in (79).

steps of the hydrogenation

[207].

of

371

NT

I

(C0)4Ru \

-Ru(C0)3

\/

4 RU,H

(cob

79

7b The rate of dehydrogenation equilibrium

between in water

explained

by the formation

charge

results

solution.

The profound

of the stoichiometric

has been studied

support

the following K olefin -

H2Rh@Ph3)3C1

promote

ionic

of cations

by reducing

dimerization hydrogenation

with different

and the

at different

influence

of ion pairs which

of the Co species

The kinetics H2Rh(PPh3)3C1

to Co(CN)z-

the two species was studied

strengths overall

of HCo(CN)z-

olefins

is

the

[2081. with and the

mechanism:

H2Rh(olefin)(PPh3)2Cl

k

pPh3 k

-

~~h(dLkyl)(pph~)~ci

q-

*(pph3)3c1

The values

of K for substituted

withdrawing

power of the para

intramolecular verse

trend

reveals

migratory

insertion

intermediate

PPh3 ligands

in cis position

hydrogenates

3,3-dimethyl-1-butene

References p. 435

rate constant

cycle of hydrogenation

slower

with

k follow

the re-

with olefins

contains complex

in a stoichiometric analogue

of the

to H2Rh(PPh3)3Cl

reacting

probably

12101. The binuclear

than its mononuclear

the electron

and the values

of DANTE techniques

that the bis(phosphine)

significantly

increase

substituent

[2091. Application

in the catalytic

styrenes

+ a-

the two (80)

reaction

(81) E2111.

372

s =MeoH

81

80 The structure

of ts,Ir(Me,CO)(Pah3)21BF4,

for the dehydrogenation

of alkanes

[212]. A general

for the distinction

method

and heterogeneous Soluble

hydrogenation

and cross-linked rings were

hydrogenated

in the presence

geneous

PF6 and Rhz(C5Me5)2C14 geneous

compared

of anion

for hydrogenation. exhibited

(Et3P)ZPt(neopentyl)2

either pentane

10.

addition

were

olefin

l2l.31.

studied

activity

by ESCA

of these

with OH forms of ion (Et3Pj2PtH2

of Et3P the rate limiting

on the first order

rate limiting

step is

In the presence

of H2 to Pt or more probably

from Pt becomes

hetero-

[214].

of Et3P from the complex. depends

bonds

like a heterorings

reacts with H2 and yields

In the absence

the rate of reaction

acted

exchangers

activity

whereas

as a homogeneous

of aromatic

Pd complexes

highest

double

that they are

this test, [WCOD) (m~)pyl

with the catalytic

exhangers

the dissociation

catalysts

using

homogeneous

olefinic

but the Eh complex

complexes

and neopentane,

containing

in the hydrogenation

Pd complexes

and the results

between

and it was found

of soluble

catalyst

was determined

has been developed.

were found to behave

catalysts,

catalyst

Several

prepared

are ineffective.

catalysts

hydrogenating

catalysts

polymers

and aromatic

an active

ar alkenes,

of Et3P

of HZ pressure

elimination

and

of neo-

12151.

Dehydrogenation Photocatalytic

ence of

dehydrogenation

of iPrOH proceeds

(NB416M0703~. QH30. A reduced MO species

which was characterized react at 70°C with

spectroscopically

H7Re(PPh3j2

in the pres-

is also

formed

(2161. n-Alkanes

and 3,3-dimethylbutene

(C6-C5)

to afford

373 equilibrium

mixtures

of the corresponding

hydride

complexes

at 60°C

into l-alkenes

(diene)-rhenium

(82). These latter are transformed

tri-

by P(OMe)3

[217]:

+-

R---b4.zQk+~ L>R
L2ReH3 \

L>R;H3 J

V

82

L = PPh3

P(OMe)3 RH2 is produced tions of ascorbic

catalytically,

HPd(PEt&

Photochemically

electron

to the Pd complex

product

is dehydroascorbic

Primary presence

alcohols

acceptor

to aldehyde

as catalyst

___c

RCOOCH2R

+ 2 AH2

or ketones may serve as hydrogen

of the hydrogen

and alcohol

Ziegler catalysts

prepared

at 150-200°C.

Homogeneous

react and are

have been achieved

also requi-

from Co or Ni acetylacetonate

dehydrogenation

of cyclooctane

and to

[2201. to cyclo-

of Ir and Ru poly-

of 3,3_dimethylbutene

(45-70 catalytic

with H51r(PPri)2,

of tetraline

inhibit the reaction

by means of a variety

at 150°C, in the presence Best results

The reaction

[219.].

the dehydrogenation Phosphines

catalytic

octene has been effected

acceptor

in

is dehydrogenated

to form the ester. This latter reaction

iBu8Al or iBu2AlH catalyze

Referencesp.435

acetylene.

in the first, alcohol

and in the second, aldehyde

res the presence

pre-

stoichiometry:

of a small amount of diphenyl

dehydrogenated

-acceptor.

an

The organic

at 145OC into esters in the

(A) and RUDER

and aldehydes

takes place in two steps:

hydrides

transfers

the best results were achieved with cyclohexanone

the presence

naphthalene

[Ru(bpy)5]+

solu-

and

[218].

to the following

olefins

acceptors,

produced acid

2 RCH20H + 2 A Acetylenes,

of aqueous

from which H2 is evolved.

are transformed

of a hydrogen

cursor according

on photolysis

acid in the presence of [Ru(bpy)3]2+

turnovers

as H-

in several days)

H51r[P(C6H5F-p)312

and

374 The reaction

H4RufP(C6H5F-p)313. but appeared

to be perfectly

hydrogenation irradiation between

(TPP)RhCl

as catalyst.

in the photoexcited

in the photocatalytic

orbitals

also quantum

the process

Two molecular

orbital9

pair of unoccupied phases

and the

with both H-H and Rh-H bonding

of other

+ PPh3

Rh(I) complexes

is less active

under

after

expo-

these condi-

[224]. p -Amino

presence rated

ketones

reaction

to give

in the

U,P-unsatu-

[225 1:

Transfer -p-W-

Alkanes

Complexes (~-Fc~H~)~P]

as Hydrogen

of the type

to arenes

cyclooctane

The dimeric

[H21r(Me2C0)2L2]SbF6

[L = PPh3 or

at 85-150°C

In the presence

to cyclooctene

can aromatize of a base

[226].

of C=C bonds

titanocene

in unsaturated

(83) catalyzes

hydrocarbons.

into saturated

olefins

predominantly

yield

of tBuCH=CH2

in good yields.

proportionate [227].

Donors

is dehydrogenated

Hydrogenation

H-transfer

Reactions

in the presence

cyclohexanes

b)

by PdC12(MeCN)2

[334, 3731

Hydrogen a)

are dehydrogenated

of Et3N in a stoichiometric

aminoketones

See also

tar

states

of H2 from iPrOH can be achieved

and a number

sure to air. RhC13.3H20

11.

to describe

the symmetric

[223]. Photogeneration

Rh(PPh3)3C1

reaction

[222]. This bimolecular

chemically

orbital9

de-

light

and ground

and Rh-H antibonding

pair of occupied

brown

Liquid-phase

A bimolecular

and Rh-H bond breaking.

as important:

with H-H bonding

symmetric

cycle

gradually

under visible

complexes

of H-H bond making

tions

proceeds

with

was studied

phases

[22X1.

homogeneous

of iPrOH to acetone

were designated

with

turned

(TPP)RhH

is involved process

mixtures

the intermolecular

Cyclic

and aromatic linear alkanes

hydrocarbons

hydrocarbons

dis-

while

and high molecular

linear weight

375

83

Cocondensation cyclohexene-1

of chromium

results

the corresponding The mechanism

atoms with cyclohexene

in hydrogenations

cyclohexanes

and aromatic hydrocarbons

of the transfer hydrogenation

as H donor and trans-Mo(N2)2(dppe)2 metric

reaction

active species

of 1-hexene with MoH4(dppe)2 precursor

to

[2281.

of 1-hexene with iPrOH

has been studied. The stoichio-

in transfer hydrogenation

formed from the catalyst

or I-methyl-

and dehydrogenations

suggests that the

is MoH2(dppej2

which is

by its reaction with iPrOH

[2291.

Kinetic transfer indicated

investigation

hydrogenation

of unsaturated

that the catalytically

This species coordinates within

of the Ru2[(-)-DIOP]3C14

the complex

-catalyzed

acids and esters by alcohols

active species is Ru[ (-)-DIOP]C12.

the substrate

and H-transfer

Polystyrene-bound

IrC1(CO)(PPh3)2

formic acid to a variety

of olefinic

promotes

H-transfer

from

Detailed

kinetic

substrates.

studies were carried out with benzylideneacetophenone The essential

takes place

[230].

steps of the mechanism

as proposed

as H-acceptor.

are illustrated

below:

HCOOH

-

The fully activated proof

Lnlr

catalyst

[2311. Transfer

a, p-unsaturated by Ir(CO)(PPh3)2C1

Referencesp.435

Lnlr’1

+ -ftH

L

-

L

l

CO2

H

is air stable and essentially

hydrogenation

of the olefinic

ketones by formic acid is copolymer.

than the homogeneous

eff.iciently catalyzed

The anchored

complex

leach

double bond of

reacted with a diphenylphosphinated

linked styrene-divinylbenzene more reactive

-

12321.

0.02 crosscatalyst

is

376 Hydrogenation

c)

Aldehydes yields

of C=O Bonds

and ketones

by transfer

hydrogenation

and ruthenium-phosphine No solvent

the diol is transformed

The thermally transfer

radiation.

into

The active

rated HCo[PPh(OEt)213 from Rh2(COD)2C12,

species

is probably

[2341. Catalyst

KOH,and

[2351. A similar

alcohols

bidentate

catalyzes under

coordinatively prepared

phosphines

stereoselectivity

0

to ketones

systems

by

as H-donors E2331:

+

HCo[PPh(OEt)214 alcohols

(n= l-4) proved to be active in the transfer cyclohexanones with refluxing iPrOH. Mainly formed

is not limited

2 RCHOHR’

inert complex

as H-donor as catalysts.

y -butyrolactone

-

from secondary

with high

1,4-butanediol

like HRuCO(PPh3)Cl

as it is in the case of secondary

2 RCOR’ + HO(CH2)4OH

hydrogen

using

complexes

to alcohols

has to be used and the conversion

equilibrium because

can be reduced

the ir-

unsatuin situ

Ph2P(CH2),PPh2

hydrogenation of alkylcis alcohols were

was observed

if PPh3 or

PBu3 were used as ligands L 2361.

X = MeOH,H Cl ,NO2 Y = H,Cl

85

84

n = 2,3

87 86(o-,m-,

and

p- isomers)

371 H-transfer reactions from iPrOH to acetophenone or cyclohexene are catalyzed by neutral R~(I) complexes of the type Rh(COD)L and Rh2(COD)2L'

in the presence of KOH. L (84,85) and L' (86,87)

are Schiff base ligands. The catalytic activity of these systems is lower than that of related cationic ones [237]. Transfer hydrogenation of aldehydes and ketones by sodium for-mate under phase-transfer

conditions takes place according to

the following equation: RR'CO + HCOONa + H20

RR'CHOH + NaHC03

-

Ru(PPh3j3C12 was found to be the best catalyst for aldehyde reduction and a 1:lO mixture of Rh(PPh3)3C1 and PPh3 showed the highest activity in the transformation of ketones [2381. Complexes of the type [Ir(HD)(L)C104]

(L = substituted phenanthroline

lyze the H-transfer from cyclopentanol

ligands) cata-

to 4-tert-butylcyclohexanone

following pseudo first order kinetics. The covalent analogues Ir(HD)(L)X

(X = Cl, Br, I) are less effective catalysts

[2391.

Transfer hydrogenation of ketones and aldehydes by methanol as donor is catalyzed at temperatures around 150°C by C5Me5 complexes of Rh and Ir, 0sH(Br)CO(PPh3)3,

and Ru(PPh3)3C12. MeOH is trans-

formed into methyl formate,and the reduction thus may be described by the equation 2 R2C0 + 2 CH30H The iridium complexes

-

2 R2CHOH + HCOOCH3

[Ir(COD)L21+

[2401

(L = tertiary phosphine) are

very active catalysts for the transfer hydrogenation of cyclohexanone and 4-tBu-cyclohexanone

with iPrOH. At the start of the reaction turnover numbers above 1000 S -1 can be observed, tha catalyst is,however, rapidly deactivated

12411. The system formed in

situ from Ir2(CODj2C12 and P(C6H40Me-g)3 catalyzed the selective (90%) transfer hydrogenation

of the carbonyl group in 5-hexen-a-one

by iPrOH. The yield of unsaturated alcohol increased with the P/Ir ratio.Other phosphines and unsaturated alcohols tested gave less satisfactory results [2421. See also [187].

Referencesp.435

378

d)

Hydrogenolysis

Enol triflates tributyl

amine

like

as catalyst

(89). A valuable

tive and quantitative

Transfer

(88) may be reduced

(tributylammonium

Pd(OAc)2(PPh3)2 alkenes

by Hydrogen

fonnate)

with

formic acid and

in the presence

of

at 60°C in DMF to the corresponding

feature

of the method

introduction

is the regioselec-

of a D atom if DCOOD

is used

[2431.

80 %

89

88 The complex on a fused

silica

hydrogenation the transfer

(~-Cl)[V-SCH2CH2Si(OEt)31

Rh2(C0)2(PBu:)2

support was used as catalyst

a, p -unsaturated

of

hydrogenolysis

ketones

for the transfer

with

of trihalomethyl

fixed

formic

acid and

compounds

with

iPrOH

12441: PhCHCC13 I OH

12.

Reduction a)

-

+ Me2CHOH

without

Transition

Molecular

Metal

Acyl chlorides

can be selectively

In the presence

equivalent 6 anionic

of hydride

aromatics

aldehydes

reduced

by group

under mild 6B anionic

as deuterium-transfer The deuterides by exchange

of acid the aldehydes

and are reduced

do not interfere

deuterides

DM(CO)i

hydrides

is nearly

consume

to alcohols.

Alkyl

with the reaction

quan-

a second bromides

[2451. Group

for the reduction

used

of organic

halides.

in situ from the corresponding

hydrides

[246]:

R-Br + BM(CO)i

condi-

(M = Cr, W) may be conveniently

reagents

are generated

with MeOD

+ HCl

HydroE

(M = Cr, W; L = CO, PR3). The reaction

titative. or nitro

+ Me2C0

Hydrides

tions to the corresponding RM(cG)4L-

PhCHCHC12 I OH

MeOD TBF -

R-D

379 supported

HFe(CO)i reduces

on an anion exchange

acid chlorides

reflux

temperature

regioselective

reduction

(90) to 1-acyl-1,4_dihydropyridines

copper

hydride

reagent

prepared

0‘i?‘I ct-

l-acylpyridinium

(91) was achieved

by a

and CuBr

[2481.

I

I

91

!203,209,2111.

b)

Low Valent

Amine

N-oxides

Transition

compounds

Metal

were reduced

[2491. Aldehydes

hydrocarbons

or ketones

by Cp2Ti(CO)2

[250]. Reduction

in aqueous

to amines with TiC13 were reduced

substituted

in over

to alcohols

products

60%

and

THE‘. Some aromatic

coupling

of halides

DMF containing

n = 4 and n = 5 cases

Complexes

in reffuxing

'yielded also reductive

pinacols Cr(II)

A261

in THF at

6, R&l

-

90

yield

of

from LiAlH(OBut)8

R&l

See also

(Amberlyst

aldehydes

[247].

The completely salts

resin

to the corresponding

carbonyl

like olefins

of the type RCaC(CH2)nX

ethylenediamine

yields

or

with

in the

methylenecycloalkanes:

Cr(II) RC=S(CH2&X

Experimental mediate

conditions

radicals

result

ment with chromous reductive

whdch

dimerize

RCH=CyH21n

favor

longer

in-increased

chloride,

elimination

spontaneously

-

cyclization

affokrding g-quinodimethanes or may be trapped

[

Beferenceap.435

(92) undergo

(93) which

with dienophiles

/a 93

for the inter-

12511. On tr&at-

cl ,d -dibromo-o-xylenes

\

92

lifetimes

CH2 CH2

either

[252].

380

Benzenethiosulfonate phenyldisulfide product

(94) is reduced by (NH4)2(Mo2S12)

in refluxing

acetonitrile

is formed from benzene

oxidative

coupling

with 81% yield. The same

sulfonyl chloride presumably

followed by reduction

PhS02SPh

to diby

[2531.

-

PhSSPh

-

PhSSPh

94 2 PhSO2Cl

Alkyl-Mn(IIf

compounds

(prepared in situ) deoxygenate

epoxides

to olefins: 0

1. bin

(II) c

%%

2. H20

MeMnCl or Bu3MnLi are used as reductants reactive reagent

[2541.

Propargylic

methyl

ethers

the latter being the more

(95) and acetates

(96) were trans-

formed with an ethyl cuprate, derived fran EtMgBr and CuBr.Me2S reduction

(97,981 and substitution

(99,100) products.

esters gave rise to more reduction

into

The methyl

products than the acetates

[2551

ME!CH~+EtC=oCy 98

97

95, 96,

R = Me R = AC

+MeCWc=c

/

Et

\

F + MeCHCzq

CY 99

cl

Inorganic Reductants

100

in the Presence of Transition

Metal

Complexes Alkenyl

sulfides were reduced to the corresponding

alkyl

sulfides with HSiEt3 in the presence of TiC14 with good yields.

381

The reduction proceeds through the formation of an alkyltitanium intermediate

[2561.

Systems composed of molybdate L-cysteine or aminoethanethiol

and thiol ligands such as

are effective catalysts for the

reduction of hexynes to the corresponding

hexenes and hexane by

NaBH4 [257]. Reduction of sulfoxides, sulfonyl-sulfilimines tinamide

sulfilimines

(101) and p-toluene-

(102) by NaBH4 or 1-benzyl-1,4-dihydronico-

(BNAH, 103) is catalyzed by Fe(TPP)Cl or Co(TPP). Best

results were obtained with the Fe(III)(TPP)/BNAH

”

-

system [2581.

'S'

NTs lo1

102

CONH2 103 I 6H2Ph Olefins

(104) and (105) were reduced with Zn + XOH

lytic amounts of cob(I)alamin. was able to differentiate

and cata-

If reduction was slow the catalyst

the two diastereotopic

faces of the endo-

cyclic double bond in (105) [2591.

\

tBu u

Cob(I)alamin

R=CN,

also catalyzed the reduction of aldehyde

with Zn + AcOH to the cyclopropanols

Referencesp. 435

CMe2 R

(107) and

CH20H

(106)

(108) [260].

382

CHO OH tBu 106

107

108 Alkenes

can be hydrogenated

using NaBH4 in the presence of

CoC12 in a mixed THF + MeOH solvent. vent, hydroboration aryl-substituted

If only THF is used as sol-

is the main reaction

[261]. The reduction

ketones with Et4NBH4 is catalyzed

the influence of visible

light. Deuterium

monoxide

[262]. Reduction

complexes

transferred

of nitrosobenzene

was carried out in the presence

sobenzene

as catalyst.

by Co(TPP) under

labeling experiments

show that the H of the BH; anion is directly Cc-carbon atom

to the

with carbon

of Rh(1) or Ru(I1) nitro-

In ethanol the reduction

proceeded

already at 75OC and 1 bar, in benzene more drastic conditions needed. Azoxybenzene Complexes

[263].

of polyethyleneimine

with PdC12, RhC13, NiC12, CoC12

the hydrogenation

of 1,3_cyclohexadiene

or NaBH4. The order of activity of the metals [264]. Reduction

were

was the main product but a wide range of

other compounds was also formed and RuC13 catalyze

of

of propargylic

is Pd>Rh>

halides or esters

with H2 Ru> Ni,Co

(109) to allenes

(110) with hydride donors in the presence of Pd(0) proceeds best if Et3BHLi

is used for the reduction X

H-

R-C=C-Cc

c \

109

R'

of mesylates:

R-CH=C=CR'

-I-R-C'C-CH2R'

Pd(PPh3)4 110

Ill

R' = Br, OMs Acetylenes

(111) are formed as byproducts

[265].

383

The combination oximes

of NaBH4 with NiC12.6H20

into saturated

the presence Aromatic

amines.

nitro compounds

acids to N-substituted

ence of a catalytic

using

may be used

Reduction

Instead of SnClq other Lewis acids like [2671.

of Carbonyl

Compounds

of acetophenone

37 different

chiral N-chelating

or K[PtC13jC3Hq)l

tion in the presence

these ligands.

(109-112).

Enantioselectivity the optical

after hydrolysis. rhodium

via Hydrosilylation

with Ph2SiH2 was investigated ligands

as Catalysts

of 21 different

containing

by determining

E2661. N-acylated

amides at 180° in the pres-

Hydrosilylation RhZ(COD)2C12

intact

are reductively

amount of P+~fPPH3)~c12 combined with SnCl.$,

under 60 bar CO pressure. FeC13 or AK13

unsaturated

is carried out in

of Moo3 the C=C double bond remains

and aliphatfc

by carboxylic

d)

converts

If the reduction

in combination

or performing

Rh or Pt complexes

the reac-

already

Some of the ligands used are shown below of the catalysts

purity of

was characterized

c -phenyl ethanol obtained

Highest o.y. was 79% obtained

with

(109) and

[2681.

110

109

c-k N H

CH2/

NHyf!Y;

111

References p. 435

\

Ph

with

Ma,

wl~_~/Mo Me \ ‘L)-H

HdC_N/

N-C”

‘Ph

Ph’ 112

384 e)

Organic

Reductants

in the Presence

of Transition

Metal

Complexes The oxomolybdenum the reduction

of Me2SO Me2SO

This

system models

enzymes

complex

MoO(L)(D~~

by PPh3:

+ PPh3

Me2S + PPh30

-

the mononuclear

that catalyze

(LH2 = 113) catalyzes

oxygen

active

atom transfer

site of certain reactions

molybdo-

[2691.

113 Various tuents were

nitroarenes reduced

in high yields as catalyst.

having

chloro,

formic

Heterocyclic

acid in the presence

compounds

quinoxaline

could also be reduced

RuC12(dpm)2

catalyzes

allylic

alcohol

saturated

with cyclohexene the reduced accelerated flattening C=Of4f

+ HC02Na

and PrCHO

flavin

by divalent

N , P-Unsaturated saturated

nicotinamide

[271]. The reduction

metal.ions

the 1,5_dihydroflavin

indole,and

( Co2t

molecule

[270].

1-heptene

and

at 25-30° to give the

The reaction

(114) in EtOH under anaerobic

and N(5) positions

sponding

in water

in high yields.

aminoarenes

such conditions

of l-hexene,

substi-

of RufPPh3)3C12

such as quinoline,

under

the reduction

by HC02H

products

ox methoxy

to the corresponding

at 125-180*C

using

methyl

Wi2+r

is less efficient of p-ClC6H4N02 conditions Mn2+ )

which

via coordination

with

Is act by

at the

f2721.

carbonyl

carbonyl

(an NADPH model

compounds

compounds compoundf

are reduced

to the corre-

by N-propyl-X,4-dihydrowith the aid of RhfPPh3f3Cl.

335 The reduction

was accelerated

by the addition of an equivalent

amount of LiClO4. The system is ineffective u,p

-unsaturated

corresponding

esters

for the reduction

[2731. Aryl iodides are reduced to the

arenes with N-benzyl-1,4-dihydronicotinamide

model of NADPH) in the presence of Hh(PPh3J3C1 carbonyl,and method

ester functions

is also applicable

Dimethyl

diazomalonate

with R~(OAC)~

of

as catalyst.

Nitro,

are inert under these conditions.

for the reduction

of vinyl halides

smoothly deoxygenates

as catalyst

(also a The

[2741.

epoxides to alkenes

in toluene solution at reflux tempera-

ture:

c

,COOMe 0 + N2C blOMe

>

-

,COOMe

+ oc

I

‘COOMe

Yields are above 75% 12751. Aryl bromides

are conventiently

alcohol and NaOH in a two-liquid

dehalogenated

with benzyl

phase system in the presence of

Pd(PPh312C12: ArBr + PhCH20H + NaOH

-

ArH + PhCHO + NaBr + H20

Phase transfer catalysts

significantly

reaction

allylic compounds

[276]. Terminal

phenyl ethers, carbonates, genolyzed + PBu3

by ammonium

chlorides

enhance the rate of the like allylic esters,

and vinyl epoxides are hydro-

formate to give 1-alkenes by using PdC12

(Pd:P = 1:4) as catalyst

[277]: H

R/\\/\X X =

R A#@

-

OAc, OPh, OCOOMe, Cl.

f)

Electroreduction

Carbonyl chemically

compounds

are reductively

or electrochemically

dimerized

reduced tungsten

[WI 2 >=o

20°C, N2

Referencesp.435

>="

+

into olefins by species:

[wlo2

Best results

are obtained

electroreduction stilbene

by means

quantitatively

of WC+,

yield

chemical

reduction

alkenes

of stilbene

is added after

is very

iscathodically

is catalyzed

gives

generated

esters

12781. The electro-

to 1,5-hexadiene

cleavage

by Pd(PPh3)4.

of allylic

the electroreductian

low, however

of ally1 halides

which

the conversion acids

PhCHO

L2791. Electroreductive

cycled

potential

Benzaldehyde

(mainly E) when THP is used as the solvent

and Al as the anode. When

by Ni(PPh3)4

of a controlled

of WCls at a Pt electrode.

is catalyzed

and continuously

of allylic

The method

re-

acetates

into

can also be used for

into the corresponding

carboxylic

[280]. If the electroreduction

carried coupling nolysis

of ally1 or benzyl

out in the presence

of Cu(acacj2,the

products (R-R) is increased products

(R-H). Analogous

affected

by the copper

See also

[185].

additive

bromides

yield

at the expense

chlorides

(R-Br) is

of reductive of hydroge-

or iodides

are un-

[281].

IV. -Oxidation 1.

Catalytic

Oxidation

of Hydrocarbons

or Hydrocarbon

Groups

with O2 .-General

a)

The rate of oxidation presence toluene

of CO(OAC)~ > n-paraffins

the oxidation

complex

> isooctane

of hydrocarbons

found to be olefins n-alkanes

of hydrocarbons

+ NaBr decreases

catalysts

12821. The relative

using a cobalt-bromine

= alkylaromatics

[283]. The effect

> cycloalkanes

of Co2+,

on the oxidation

complexes

Water

rate

b)

the oxidation

Oxidation

The oxidation stearate

O2 in the >

rates

for

catalyst

were

> isoalkanes

>

Br- and H20 in cobalt-bromide

of hydrocarbons

Only the low Br- containing reduced

at 90°C with

in the order m-xylene

were

was examined.

found to be active.

[284].

of Alkanes of pentadecane

+ Pb stearate

catalyst

with up to 97% selectivity

at llO°C in the presence

mixture

of a Cr

gave acids and ketones

[285]. The selectivity

in the oxidation

387 of saturated hydrocarbons by 02 in py + AcOH in presence of the soluble iron complex [Fe(II)Fe2(III)O(OAc)6Py3l2Py

and Zn is

strongly dependent on the reaction conditions. Using air and slow stirring,adamantane positions

is attacked almost exclusively at the secondary

[286]. Oxidation of cyclohexane was investigated with

mixtures of Al-, Co- and Cr-stearates as catalysts. Best results were obtained with Al + Co [2871. See also C3891..

Oxidation of Olefins

cl

The reactivity of alkenes in the catalytic oxidation to glycol esters at 135-170°C in carboxylic acid solvents using transition metal

(Ti, Mn, Fe, Co, Ni, Cu) complexes as catalysts increased in

the order CH2=CMeCH2CMe3 < l-heptene < cyclohexene

[2881. The hydro-

zirconation and following oxidation of styrene gave both FhCH2CH2OH and PhCHMeOH [289]. The liquid-phase oxidation of 1-nonene in the presence of cyanides of molybdenum

(0, II, and IV) proceeds by two

paths, one involving an intermediate catalyst-hydroperoxide and the other an complex

complex

intermediate catalyst-hydroperoxide-substrate

[2901. The rate of 1-nonene oxidation increases in the

order of catalysts K~[Mo(CN)~I c K4[MoOZ(CN)41 c K4tMoO(CN)41 c K4[Mo(CN)41

12911. The catalytic activity of group VI transition

metal carbonyls in the autoxidation of methyl oleate and decomposition of Me oleate hydroperoxide

at 80°C to form epoxy and hydroxy

compounds increases in the order W(CO)6 c MOM

< Cr(C0)6

L2921.

The oxidation of substituted olefins with O2 using a [tetrakistp-methoxyphenyl)porphinlMnCl

+ NaBH4 catalyst system has been stud-

ied. The rate and extent of oxidation increased with the degree of substitution at the double bond [2931. The oxidation of 2,3-dimethyl '-2-butene,

isobutene and 2-methyl-2-pentene

2,3-dimethyl-2-butanol,

gave regioselectively

tBuOH and 2-methyl-2-pentanol,

respectively

L2941. Oxidation of U -pinene by O2 with Co-naphthenate as catalyst gives -trans-verbenol and verbenone [2951. Cobalt ion-exchanged faujasites X have been treated with 1,2_dicyanobenzene or dimethylglyoxime. Co(phthalocyanine)

and Co(dmg), were formed and prefen-

tially located within the cages of the faujasite network. The encaged Co complexes catalyzed the oxidation of propene to acetone, acetaldehyde and formaldehyde [296]. Aryl olefins can be trans-

Referencesp.435

338

formed

into benzylic

presence

alcohols

of a catalytic

I

Ar-C=C

by the use of 02 and BHq in the

amount

BH;,

/ \

Detailed strate

the overall peroxide,

the autoxidation H202 and water, diene

[299]. Oxidation Rh(1)

complexes

eliminated solvent

at 65-80°C with as the major

studied with

added

Heteropolyacids system.

Among showed

to alicyclic

alkali

verbenol

could beused

ketones.

containing See also d)

preparation

substrate

activity

of

was cyclohexenyl

in an organic gave verbenol

earth chlorides.

were obtained

Best yields

with LiCl

in the Wacker

or

was also 13021.

catalyst

the PdS04 + H3PMo6W6040

for the oxidation turnover

by ethene oxidation

of cycloolefire

with respect

was developed

PdC12 and iron nitrate

and

was observed

The hydroperoxide

as catalyst

examined

by

in the presence

product

Ci-pinene

as oxidants

model

to octanone-2

[3011. The same oxidation

The largest

85 [303]. A mathematical monoacetate

of

and alkaline

the combinations the highest

and O2 [2981. The mechanism of octene-1

The main

and carvone

for

hydrocarbons,

with the solvent

PdC12 + CuC12 products

catalyst

of alkyl hydroper-

has been studied

period.

ethanol

of 1-phenyl-1,3-buta-

by cumyl hydroperoxide.

[3001. The oxidation

of verbenone,

system

of cyclohexene activated

ethylhydro-

[2971.

using deuterated

label exchange

the induction

hydroperoxide verbenone

alcohols oxidation

as a substeps of

into OL -phenyl

to aromatic

cleavage

investigated

Substantial

a-phenyl

and for the conversion

to their corresponding

styrene

is an effective

of 1,4-cyclohexadienes

O2 in EtOH has been

of

of acetophenone

for the selective

of the BhC13. 3H20-catalyzed solvent.

formation

that Rh2(OAc)4

to cinnamaldehyde

oxides

with

three elementary

of the hydroperoxide

and reduction

It was reported

Ar t! C< -I-\ OH

catalyzed

process:

decomposition

and acetophenone

-

of the reaction

that Co(TPP)

catalytic

O2

[co1

investigation

revealed

of Co(TPP):

to Pd was

for ethylene in acetic

glycol

acid solutions

[3041.

[305, 3911. Epoxidation

of Olefins

In the liquid-phase Ce ions catalyze

oxidation

autoxidation,

of cyclohexene

Co, Mn, Fe and

V and MO ions catalyze

epoxidation.

389

Epoxidation

via two stages: autoxidation

proceeds

hexene hydroperoxide cyclohexene In

followed

epoxide

by reaction with cyclohexene

the liquid-phase

oxidation

(115) :

to 7.4 if Mo02(acac)2

of dicyclopentadiene

(116) increased

was used as catalyst.

In the latter case

increased

the rate of oxidation

Q-JO The yields of epoxide trans- P -methylstyrene

were not influenced

system composed

complex of sulfonated were achieved

the MO complex

by Mo02(acac)2,

tetraphenylporphin.

[309]. The liquid-phase

Pt and the Mn(II1)

Several hundred

were almost exclusively oxidation

of U -methylstyrene

PhCOMe and CL-methylstyrene

first order

and 0.5 order in AIBN initiator

Co(OAcj2

catalyst.

the autoxidation were determined

This Co salt was more effective

than Mn(OAcj2

for the epoxidation

ence of benzaldehyde performed See also

e)

+ Na2C03

oxide was using

in accelerating

[310]. Optimal conditions

as catalyst.

acid coordinated

Epoxidation

is

to Co [3111.

[3541. Oxidation

of Aromatics

Several transition

metal

(Mn, Fe, Cu, Ag) polyphthalocyanines

enhance the rate of cumene oxidation, tivity to cumene hydroperoxide. uct [312]. Addition -catalyzed

of Mn(OAcj2

oxidation

from reduction

References

with

of propene by O2 in the pres-

and Co(pMeTPP)

by the perbenzoic

turnovers

monoepoxi-

air at 70-130°C yielding in PhCMe=CH2

but in

the -cis:transby a P-450 model

of H2, 02, collodial

and polyolefins

of cis- and

increased

[3081. Olefins were epoxidized

ratio

catalytic

117

formed in the autoxidation

the case of the cis-olefin

13071.

of&--go

116

115

dized

the ratio

from 2.6 (uncatalyzed)

(117) formation was less than 10% [306]. Cobalt com-

pounds and complexes

-epoxide

to form

[3051.

of the monoepoxides bisepoxide

to form cyclo-

p.435

but also decrease

Cumyl alcohol inhibits

the selec-

is the main by-prod-

CO2 formation

in the CoBr2-

of p-xylene in AcOH. The inhibition 3-k by Mn 2+ [3131. of Co

results

Hydroxylation the presence

of substituted

aromatics

of Fe2+ and ascorbic

slightly with the substituent significantly

by 02 was studied in

acid. Reactivity

varied only

but an oxygen atom in the side chain

altered the relative amount of -ortho, meta,and products [314].

para

monohydroxylated

Substituted

toluenes were oxidized

by air in AcOH, using Co

acetate as a catalyst

and NaBr or paraldehyde

most cases carboxylic

acids and aldehydes were the main products

of oxidation

as a promoter.

[315,316]. The rate of toluene oxidation

with a cobalt bromide catalyst was increased [3171. The liquid-phase ence of CO(OAC)~

oxidation

In

by 02 in AcOH

by adding HfOC12.8H20

of toluene at 75OC in the pres-

and NaBr was accelerated

by CoC12, the rate showed

a maximum

at a CO(OAC)~.*CoC12 ratio of 1:l C3181. The simultaneous

oxidation

of xylene and methyl-E-toluate

ionic Co compounds The liquid-phase

oxidation

0.5 order in catalyst

13201. In the liquid-phase [CoBr3(AcOH)l-

tivity of the anion is independent [321]. Tetralin was oxidized

per polymer chain activity decreased

with increasing on polyethylene

showed that the reaction homogeneous complexes

reaction

containing

on Si02 decreased deoxygenation

acts as

catalyst.

of the cation

of The ac-

(in this case Na) complexes

the effects of polymer mobility

In complexes

containing one metal ion

increased with chain length. Activity number of metal

Kinetic data of the liquid-phase peroxide

oxidation

by CoBr2 and NaBr the tetra-

using Co, Mn or Cu chloride

glycol to determine

and chain length on activity.

by a

was first order in tetralin and

xylene and durene in AcOH catalyzed hedral complex anion

of

[3191.

of tetralin at 65-90°C catalyzed

complex of CoC12 and polyurethane

with ethylene

by O2 in the presence

as catalysts was inhibited by E-cresol

ions per chain

oxidation

glycol-CoC12

of tetralin

complexes

13221.

to hydro-

fixed on silica gel

proceeds with the same mechanism

[323]. The rate of cumene oxidation

as in the on some Co

glycine, histidine,and O2 ligands and anchored

with increasing

temperature,

above 65OC [3241. Immobilized

plexes showed a catalytic

probably because of

Co(I1) acetate com-

effect on oxidation

of toluene at 80°C

in AcOH when dioxane was added to the solution. Co(I1) acted by promoting

the transfer of oxygen from the peroxide

to PhMe [3251. The oxidation

formed by dioxarm

of aromatic hydrocarbons

in the presence of CoBr2 was studied by redoximetry potentiometry.

The accumulation

of Co(III) was noted

by O2 in AcOH

and Br-selective [3261.

391

co3+/co2+redox

potential and O2 consumption were synchronously

recorded in the reaction mixture of the air oxidation of toluene to PhCOOH in acetic acid with a Co acetate bromide catalyst.

[3271.

Rate constants of the liquid-phase oxidation of tetralin in the presence of different Ni dioxime complexes were determined. The maximal accumulation

of 1-tetralol occured with a catalyst

containing dimethylglyoxime as anequatorial ligand [3281. Oxidation 17 O2 at room temperature in borate buffer in the of benzene by presence of the Ni(II) macrocyclic complex (118) resulted in phenol 17 0 isotope in the OH group. ESR spectra proved the containing the formation of an O2 adduct with strong superoxide character. No isotope effect was observed with C6D6 and therefore as an intermediate

of hydroxylation

(119) was proposed

[3291.

119

118

The'mixed metal acetate complex K2Pd(OAc)4 has been found to catalyze the benzylic acyloxylation

of toluene with O2 in a car-

boxylic acid as solvent at 165-17OOC: PhCH3 + RCOOH

- O2

Minor byproducts were benzaldehyde,

PhCH200CR

benzoic acid and CO2 [3301.

Oxidation of cumene in liquid phase by O2 in the presence of Cu(1) and Cu(I1) pyridine or triphenylphosphine

complexes was stud-

ied. The Cu(1) compounds act as both catalysts and inhibitors

2.

Catalytic oxidation of 0-containinq a)

[331].

Functional Groups with O2

Oxidation of Alcohols

The stoichiometric

reaction of a ,dodecamolybdo-heteropolyanion

/HPA/ in the oxidation of cyclohexanol

to cyclohexanone

and adipic

acid turns to catalytic in the presence of H202 or with aeration of

Referencesp.435

392

the reaction

mixture

by reoxidizing The oxidation

in the presence

HPA reduced

of charcoal.

H202 and 02 act

in the reaction with the substrate

of 2-ethylhexanol

in the presence

noate at 90°C gives 2-ethylhexanoic

[3321.

of Co 2-ethylhexa-

acid with up to 90% selectivity

[3331. Methylcyclohexanols catalysts

can be dehydrogenated

and O2 at 85OC. The dehydrogenation

with Rh-phosphine proceeds

faster in

the case of the less stable -_ cis isomers [3341. Cyclohexanol was to cyclohexanone by O2 in the presence of RhC13.3H20 under

oxidized

acidic conditions. conversion. conditions

The addition

of FeC13 promoted

Water was formed in equimolar RR'CHOH

were oxidized selectivity

at 70°C and 1 bar of O2 to give RCOR' with high

using catalyst

complex has been prepared

systems containing RhC13 or [Rh(H20)6]X3 [3361. A homonuclear

from a homobinuclear

Cu(II)-Cu(1)

di-k -hydroxo-

Cu(I1) complex and tetramethyl-p-phenylenediamine.

mixed-valence

complex acted as catalyst

hols with O2 to aldehydes and benzylic

CuCl and nitroxyl primary

[3351. Second-

[R = Me; R' = Bu, hexyl, octyl; RR' = (CH2)5]

(X = BF4, C104) and BiC13 and LiCl

allylic

and under optimum

40-45% yield of ketone could be achieved

ary alcohols

bridged

the catalytic

amounts

alcohols

alcohols was realized

is generated

of alco-

oxidation

by O2 using a catalyst mixture

(120) was reported.

these latter conditions

in the oxidation

[337]. The room temperature

The new

of

A more general oxidation

by CuC12 mediated

a base is necessary

of of

by (120). Under

to take up the HCl that

[338].

120

t, .

See also b)

[360, 5321. Oxidation

of Phenols

Several catecholato

complexes

base as ligand were prepared genation

of catechols

VO(acac)(OMe)2

containing

and tested as catalysts

[339]. Binuclear

catalyze

to 3,5-di-tBu-g-quinone

of vanadium

the oxidation

vanadyl(IV)

a Schiff

for the oxy-

complexes

of 3,5-di-tBu-catechol

(122), 2,4-di-tEiu+muconic anhydride

like (121)

(123)

393

and 4,6-di-tBu-2H-pyrane-2-one

(124) by 02.

122

123

121 The main product these V complexes

case of unsubstituted the corresponding

of the reaction

act in a manner catechol

cleavage

cleavage

of catechols.

is (123) indicating

similar

Reacting

catalyzes

salts of the

(3,5-di-tert-butylcatecholato)ferrate(III) cleanly dative

complex

cleavage

the corresponding

Fe(bpnp)C12

of catechol muconic

trum of the complex

lar to those observed

(nitrilotriacetato) with

1802,

into the product

(Hbpnp = 125) catalyzes

(121) by O2 in nitromethane

acid anhydride

shows changes

[3401.

the oxidative

dianion

a single 180 atom is incorporated

The iron(II1)

In the

as substrates

could not be detected

complex

that

to pyrocatechase.

or p-phenylenediamine

product

The Fe(III)-nitrilotriacetate

124

[3411. the oxi-

to give

(123). The visible

during

oxidation

which

with the enzyme pyrocatechase

spec-

are simi-

[3421.

125

Several

Co(I1)

the oxidation Homonuclear

complexes

of guaiacol

Cu(II),

and Pd-Cu complexes

Pd(II),

for the oxidation

oxidation

of

> Fe(TPP)Cl

References p.435

of

solutions

as catalysts.

in the stated order.

of (127) relative >

Mn(TPP)Cl.

catalyze [3431.

and heterodinuclear

were prepared

(121) to (122)[3441.

and VO(TPP)

decreased

ity for the formation VO(TPP)

and Cocsalen)

Pd-Ni

and used as

The rates of

(126) by O2 in DMF have been investigated

Mn(TPP)Cl

the catalysts

Zn and Co(I1)

of methylmethionine

catalysts Fe(TPP)Cl,

like Co(acac)2

by air in basic water

with Co(TPP),

The activities

of

The order of selectiv-

to (128) was Co(TPP)

The results were

Z+

interpreted

394

with a mechanism required

in which an intermediate

for the formation

dioxygen

complex

is

of (127) but not for that of (128)

L3451.

oQ-@

y&qJ+ 0 126

127

The dicopper(I1) styrene and oxirane

complexes

128

129 and 130 were anchored

acrylic beads and used as catalysts

oxidation

of catechol

complexes

was less than that of their homogeneous

(131). The activity

to polyfor the

of $hese supported analogues

[346].

CH3

x= Cl, OH \'

(

= amj~~~acid; lysine (129)

N

a N\/\/

0 glutamic acid (130)

,cu\/cu\ > 0 x 0

/0

0

QH

OH

\

6 + 0

+

11202

-

H20

131

Autoxidation diamine

complexes

phenyldiols

was investigated.

(132). Depending

the secondary (134) L3471.

of phenols with O2 catalyzed Primary

by Cu (II)-ethyleneproducts were 2,2'-bi-

on the bulkiness

of the substituents products were either a benzofuran (133 ) or a dioxepin

395

133

132

OH

OH

OH

Me

Me

134

cl

Oxidation

of Aldehydes

On the basis of earlier oxidation metal

ions as catalysts The kinetics

mechanism

of the complete

by coupling

degraded

oxidation

involving

by atmospheric

below:

2Fe(III)

D-erythrose

2Fe(II) + 2H+

+ FeC13 and D-fructose

+ MnC12

Chemical the presence oscillation

to catalytic

oscillations of CO(OAC)~

is quenched

dized to CL -diketones

Referencesp.435

oxygen

proceeded

cycle of iron ions as

D-fructose

to be susceptible

in the

13491. D-Fruc-

of FeC13. The reaction

with the oxidation-reduction

shown schematically

catalytic

of benzaldehyde

to D-erythrose

in the presence

in the

with transition

[3481.

of iron and cobalt salts was investigated

irradiation

D-Glucose

an oxidation

data obtained

by dioxygen

effects was proposed

tose was oxidatively with

experimental

of sulfite and benzaldehyde

and photocatalytic presence

and Ketones

X

H20 l/2 O2

systems were also found

photooxidation

in autoxidation

[350].

of MeCHO and PhCHO in

and NaBr involve a radical mechanism. by.hydroquinone

and oarboxylic

[3511. Ketones were oxi-

acids at 20-60°C by O2 in

The

396

aqueous-alkaline indicated

solutions

that an 02 -enol-Co-phen

liquid-phase

oxidation

with 02 catalyzed reaction

of Co-phen complexes.

by Co(I1)

of hydrocarbons

shorterohain

aldehyde.

Ketones,

among the products

of benzaldehyde

CO(OAC)~. 4H20 and C0(NAP12

nitraminopyridine).

A long induction

to the

atom

a -diketones

and

13531. The kinetics

and propene

acid and propene oxide was studied

Co(E-MeTPP),

acids

The main side

leading

or alcohols with a one-carbon

esters were also detected perbenzoic

of acyl radicals

study

[3521. The

to carboxylic

salts has been studied.

than the starting

of the co-oxidation

is formed

of several aldehydes

was the decarbonylation

formation

complex

A kinetic

by 02 to give

in the presence

as catalysts

of

(NAP = 2-

period was observed

with the

porphyrin complex which was absent with the other catalysts [354]. The kinetics of the oxidation of benzoin to benzil by O2 catalyzed by Ni acetate or Co acetate determined. nificant

The overall

in methanol

amounts of benzaldehyde

byproducts

in reactions

and ethanol have been

reaction was second order in benzoin. and benzoic

that are independent

Sig-

acid were formed as from benzil formation

[3551. 1,2-Cyclohexanediones as catalyst

to afford

roxyadipates

(135) are dioxygenated

1,5-keto

acids

by O2 with Cu2+

(136) and CO. Methyl

(137) are also formed as byproducts

a-hyd-

[356].

0 OH

135

Deoxybenzoin

(138) is converted

MeOH + O2 system to benzil Formation

(1391, bidesyl

of (140) needs only Cu(II),

cu(I1) and 02. Benzoic water

by a Cu(II)

+ PY + Ht3N +

(1401, PhCHO and PhCOOH.

that of (139) and PhCHO both

acid is formed from

(139) by Cu(II) and

[3571. I%cx+am FwH2am

138

-

PhCOCOPb+

139

L 140

+PhcHo+Phaxx

397

d)

Miscellaneous

Liquid-phase

Oxidations

oxidation

acetylacetonates

of dibenzyl

by 3d metal 2+ (n = x = 2, n = 3, x = 0; M = VO ,

M(acac)n.xH20

ether catalyzed

Cr3*, Mn2+, Mn3', Fe3+, Co2+, Co3+, Ni2+, Cu2+, Zn2+) PhCHO, PhCOOH, or PhCH20CH(OOH)Ph

yields

13581.

The oxidation

of dihydroxyfumaric acid by O2 is first order 2+ catalyst,and O2 [359]. Cobalt phthalocyanine in Fe

in substrate, adsorbed

on Si02 gel

was used as catalyst

oxalic acid and the dehydrogenation as an initiator

for the thermal oxidation products,

[3601. Co(acac)2

of diethyl maleate

well as of butyl- and methylmethacrylate sition of the oxidation

for the oxidation

of iPrOH

and catalyzes

of acts as

the decompo-

leading to additional

initiation

[361]. EDTA acts as an inhibitor solutions

containing

Autoxidation

of L-ascorbate

dine). The binding

of vitamin

between

is catalyzed

[3631. The oxidation

of a tetrabenzotetraaza gated

in aqueous

ions

is assumed

of ascorbic

macrocyclic

[362].

by Cu(II)-poly(L-histi-

Cu(I1) and poly(L-histidine)

labile at pH 4.0 and this labile Cu(I1) ically active

C oxidation

Ag+ and Pd 2+ as well as alkali

complex

is rather

to be catalyt-

acid in the presence

of copper was investi-

13641. Carboxylic

carboxylated

acids of type

into ketones

(141) or (142) are oxidatively

(143) by O2 in the presence

de-

of copper(I)

in MeCN as solvent:

R\ /-

R\CHR’/

A

R'

142 ’

141

Probably

3.

Catalytic

Cu(II1)

carboxylates

Oxidation

Autoxidation plexes of Fe(II),

are the intermediates

of N-containing

of dimethylformamide Fe(III),

oxide and dimethylamine (-)-DOPA by optically

Referencesp.436

OH

Organic

Co(II), Co(II1)

active co(II1)

Compounds

is catalyzed

are the products

[3651.

with O2

by phen com-

and Cu(I1).

Carbon di-

[3661. The oxidation

complexes

of

like [C0C1(NH3)

(ethylenediamine)2]Br2

has been studied.

proved the formation

ments

DOPA or its oxidation phenone

Optical

of an intermediate

[367]. Substituted

product (144)

phenylhydrazones

rotation measure-

Co complex

containing

2'-hydroxyaceto-

are readily oxygenated

ence of Co(salpr)

(146) in ethanol at room temperature

1,3-benzodioxoles

(145) in good yield

in the presto give

[368].

145, R=H, Me, MeO, Cl, NO2

Dihydrazones were oxidized CH2C12

of

a-diketones,

stoichiometrically

at room temperature

in good yield. Oxidation

also proceeded

CuC12 under O2 L3691. Copper(I) carboxylato

Cu(I1) complexes

the copper-catalyzed

-nitriles

of muconic

chloride

complex

acetylenes

with catalytic

of o-quinones

acids in the presence

Py

0

of

reaction

into semi-

of ammonia

02

lKuCI PY)

amounts

by O2 into the

(148). This stoichiometric oxidation

in,/' RCmCR,

adducts of the monoimines

(147) are transformed

NH

[370].

CN coocucl (py)2

148

147 The oxidation

(R = Ph, pentyl)

by the CuC12-02-py

to give disubstituted

of 9,10-phenanthrenequinones models

H2NN=CRCR=NNH2

of dimedone

bisguanylhydrazone

lyzed by Cu(I1) and the catalytic

effect increases

by air is catain the presence

399

of py. The reaction 3-coordinate

has analytical

Cu(1) complex

hydroxylation

significance

[3711. The dinuclear

(151) reacts with 02,and

of the aromatic

ring occurs

specific

in > 90% yield which

produces the binuclear pentacoordinate complex (152). Measurements 18 O2 show that the phenolate and hydroxy oxygen atoms in

using

(152) are derived

from dioxygen.

gives the phenol

Removal of the Cu ions from

(150) completing

ated hydroxylation

(152)

the sequence of the copper-medi-

of the aromatic

ring

(149) -

(150) [3721.

I cu’

ccNbRc!lNb p\

149,

R = H

150,

R = OH

Ii Dehydrogenation its substituted amounts

derivatives

could be performed

of CuBr2 at 115OC in DMF/AcOH.

the corresponding atmosphere reaction

of 5-trifluoromethyldihydrouracil

uracil derivatives

also catalytic

amounts

time was significantly

References p. 435

152 (153) and

with stoichiometric

Good to excellent

yields of

(154) were obtained.

of CuBr2 were sufficient

longer

[3731.

In an O2 but the

400 4.

Catalytic

Oxidation

Compounds

with 02

of P-, S-,or Halogen-containing

PPh3 was oxidized

in MeCN using FeX3 and

(X = Cl, Br, -NCS) as catalyst.

FeX3(0PPh3)2 increased

by 02 to OPPh3

in the order

-pentakis(methoxycarbonyl)cyclopentadienyl] phosphine

in the course

Ru(OEP)(PPh3)n OPPh3,

solvents.

of this reaction porphyrin

by the coordination

the catalytic

oxidation

of excess

probably

that generates

02 and Ru(II1).

from the superoxide are utilized

octene

D-labeled

This reaction

outer-sphere

The PPh3 is oxidized

A complex

Complexes oxidation

show that oxygen

plexes

by double Mn(II),

imine ligands

with the composition

catalyzed

Mn(II1)

catalyze

to the corresponding the sulfide

peroxide, by alcohol

of R2NCS2Na heterocyclic cobalt

carbonyl Ru(I1)

is oxidized

[380]. Rate constants complexes

hydrocarbons

by oxidation

compound.

in Me2S0

sulfides

According

by O2 com-

is

Ru(IV)

to kinetic

[382]. A kinetic

and

is reduced

for the oxidation

with O2 and different phthalocyanine

the removal

as

oxi-

by O2 to Ru(IV)

by peroxide,and

catalyze

sulfonate

hydro-

with acac or

1 mole of alcohol

were determined

of 2-mercaptoethanol

tetrasodium

of dialkyl

with

[378].

and Co(I1)

of Co [381]. Cobalt

disulfophthalocyanine

at the vinylic

chain termination

is oxidized

(R = Et, R2N = piperidino)

of the oxidation cyanine

studies,

Experiments

takes place only in alcohols

and for every mole of sulfide

and l8 -O-labeling

of cyclo-

by cis- or trans-RuX2(Me2SO)4

(X = Cl, Br). The reaction

solvents

and Ph3P0.

attacks

was

as catalyst yields

bond migration

with O2 [379]. The oxidation

can be effectively

system

13771. The co-oxygenation

cyclooct-2-ene-l-01

of Cu(II),

salicylaldehyde

reaction

by H202 formed

(OPD = o-phenylenediamine)

as an intermediate

substrate

of

of Ph3P to Ph3P0 by 02. Both 0 atoms of O2

in this oxidation.

alcohol

is

In contrast,

[376]. The o-phenylenediamine/Co(II)

gen and this is followed

dized

H2(OEP).

and PPh3 with O2 and Rh2(cyclo-octene)4C12

the allylic

by

PPh3 with O2 in the presence

[Ph3P(OPD)2Co-O-O-Co(OPD)2PPh3]4+ characterized

the oxidation

with O2 to generate

goes via an initial

the oxidation

q5-

[375]. The complexes

of O2 to Ru(OEP)(PPh3).

Ru(OEP)(PPh3)2

catalyzes

catalyzes

[L =

The ligand L is replaced

(n = 1,2) react in toluene

Ru02 and the parent

initiated

The rate of oxidation

[374]. CpRu(L),

Cl < -NCS < Br

of Ph3P by 02 in nitrile

Organic

macro-

and di-Na

of thiols

from

study has been performed

by O2 using Co(I1)

(155) attached

phthalo-

to poly(vinylamine)

as

401 a catalyst.

The stoichiometry

is the following:

of the reaction

2 EECH2CH2SH + O2 -

I-KCH2CH2SSCH2CH20H+H2°2

2 HCCH2CH2SH + H202 __L

REH2CH2SSCH2CH20H+ 2 Hz0

The polymeric

catalyst

exhibits

behavior

(Michaelis-Menten

mediates

[383].

large activity

kinetics).

and an enzyme-like

Radicals

are reaction

inter-

NaOgS 155

SO3Na

Continuous presence carried

flow epoxidation

of V(acac)3

catalyst

out at 150-170°C

in the presence

of graphite

MoC12

or MnC12

epichlorohydrin.

epoxidized

by the

OL-phenyl

plexes

yields

hydroxylation

-chloro-benzyl

alcohol

cyclohexanones

like

in methanol absence

solution

of oxygen

[387].

Referencesp.435

lamellar

ethyl hydroperoxide by air catalyzed products

into adipic

compounds

The olefin formed

(chloro-methyl-phenols),

acid dimethyl

comp-

[3861. 2-Halo-

by air and FeC13

only dehydrochlorination

is

[3851.

by hemin-thiol

and E-chloro-benzaldehyde

(156) are oxidized

with

of allylchloride

containing

Oxidation of p-chlorotoluene

phthalate,

in low yields

of a mixture

and ethylbenzene

yields

by air in the

in dimethyl

gave epichlorohydrin

[3841. Oxidation

96% selectivity

of ally1 chloride

dissolved

esters

occurs

as catalyst

(157). In the

yielding

(158)

157

158

5.

Catalytic Oxidation of Organic Compounds with Organic or Inorganic Oxidants

a)

Oxidation of Hydrocarbons

or Hydrocarbon

The complex Cr05. Ph3PO oxidizes hydrocarbons of tBuOOH to alcohols and ketones. The oxidation ic [3881. The cyclohexenones

in the presence is partly catalyt-

(159) are oxidized by K2Cr207 and air

in the presence of phosphomolybdic lohexenediones

Groups

acid and CuS04.5H20 to the cyc-

(160) in 60% yield [389].

0

R

-

0

Me Me

I

R

=H, Me

R

0

160

159

Oxidation of olefins with tBuOOH in the presence of Cr(C0)6 or Cr(C0)3(MeCN)3

produces enones by allylic methylene

The catalyst may be recovered almost quantitatively.

oxidation.

In certain

cases this oxidation proceeds selectively even in the presence of a secondary alcohol, cf. oxidation of (161) [390]. OH

OH 60%

161

403 cis-Stilbene,

cyclohexene,and

styrene,

dized with Mn(III)-bleomycin Epoxides

ascorbate). results

were quite

and ketones

similar

norbornene

were oxi-

and PhIO or 02 (in the presence were

the main

to those obtained

products

of

and the

for metalloporphyrins

[391]. Aliphatic oxidation solution

with

ketones

are converted

Na2S208

in the presence

at 80°Cl Yields

tuted alkenes

were

are around

into

of FeSO4.7H20

system.

to be an unusually

catalyst mation with

efficient

and oxidative

P-450,

hydroxylation

in most

cases.

by vanadium(V)

were

ether

p-pinene

site

of maleic,

for-

of 3,3,6,6-d4has been examined + PhIO.

rearrangement

involving

initial

13951. Rate constants

fumaric,

acrylic,and

the aldehyde

H atom

for OS&III)

cinnamic

double

with KI04 in the presence

and Os04 to yield

Turn-

of the

p -0x0 dimer

by extensive

[396]. The allylic

cleaved

agent.

and

were the primary reactions.

was suggested

determined

(162) was oxidatively -18-crown-6

was accompanied

from the allylic oxidation

against

+ PhIO and Cr(TPP)Cl

hydroxylation

A mechanism

as oxidizing

[3941. Oxidation

Fe(TPP)Cl

was found

hydroxylation

The high activity

to its resistance

and allylic

Allylic

-catalyzed

benzene

achieved.

destruction

chloride

for alkene

methylenecyclohexane,and

cytochrome

abstraction

catalyst

up to 10000 were

is attributed

Epoxidation

and disubsti-

into I_ trans-vicinal diacetates by an A mechanism was proposed [3931. Meso-

by pentafluoroiodosyl

-cyclohexene,

on

in water

50% [3921. Mono-

-tetra(2,6-dichlorophenyl)porphinatoiron(III) epoxidation

and 6 -diketones

transformed

Fe2+/persulfate/AcOH

over numbers

y-

acids

bond in of dibenzo-

(163) [3971.

MeOCH20CHCH= CH2 OMe OMe

OMe 162

Oxidation by cobalt radicals

of cyclohexene

by cumene hydroperoxide

tetra-4-tert-butylphthalocyanine. formed by decomposition

Referencesp.435

is catalyzed

The reaction

of the peroxide

[3981.

involves

404 Chlororhodium(II1) tBuOOH

complexes

in alcoholic

Olefins acetic

are converted

acid with

into allylic amount

as oxidant.

of a terminal

the oxidation

to yield mainly

a catalytic

valent of benzoquinone oxidation

catalyze

solvents

methyl

of l-octene

octanone-2

acetates

by treatment

of Pd(OOCCF3)2

The reaction

by

[399]. in

and one equi-

is selective

group of geranylacetone

for

(164) [400].

164 p -Aryl dation

carbonyl

of styrenes

are formed which lowed by Cu(I1) yields See

by S20i-

add water oxidation

the product

also

compounds

are the major

+ Cu(I1). to give

products

Initially,

radical

p -hydroxylalkyl

to epoxide.

in the oxications

radicals

Acid catalyzed

fol-

rearrangement

[401].

[469].

b)

Epoxidation

Epoxidation in the presence

of Olefins

of

(Z)-

and

(El-Me(CH2)5CH=CHCH20H

of Ti(OPri) 4 and D-tartaric

gave the epoxides

with

acid dimethyl

(165a; R, R', R2 = H, hexyl,

CH20H)

tBuOOH ester

and

(165b;

R, R', R2 = hexyl, of

H, CH20H), respectively. The enantiomeric (165b) was greater than that of (165a) [4021.

Based on kinetic

R

R'

0:: Hx

R2

tartrate-catalyzed

t-BuOOH

was discussed.

alkyl

peroxo

an important alcohols

in the transition

esters

synthesis

epoxidation

interaction

using

transformed

the Sharpless

group

of

with

asym-

The oxazole

group

Since epoxidation

method

(167) [404].

as

[4031. Allylic (166) were

method.

directly,this

ester epoxides

of olefins

was postulated

state

into an ester group.

is not possible

of chiral

TCn orbital

a 4,5-diphenyloxazole

epoxidized

the mechanism

of a lone pair of the reactive

the olefin

may be easily allylic

asymmetric

The alignment

0 atom with

containing

metrically

165

data and enantioselectivity

the Ti

excess

enables

the

of

405

167

166 The allylic presence -epoxy

alcohol

(168) was epoxidized

of L(+)-diethyl

alcohol

tartrate

(l69) with

with tBuOOH

and Ti(OPri)4

-

HOA+Cme 169

168 The alcohol of

(+)-(170)

to give

(169) was further

with Cr03/py

oxidized

in dichloromethane

was carried

Sharpless-system

to the 8S,9S-

69% yield.

HOvCOOMe

aldehyde

in the

into the corresponding

[405]. Kinetic

out at -5OOC by epoxidizing

[tBuOOH + Ti(OPri)4

(171) and unreacted

resolution

with the

+ (+)-diisopropyltartrate

(+)-(170b)

[406].

OMe

OMe 17Oa

R=OH;

R’=H

170b

R= H;

R’= OH

171

Chiral resins

tartrate

of geraniol was obtained reagent

with tBuOOH

of water

ldiethyltartrate prochiral

50-908 optical with

linked to 1% crosslinked groups

and Ti(OPri)4 epoxidation

catalyst.

sulfides yield

[407]. The

was modified

= 1:2:1:1].

into optically

reagent

This reagent active

(DET)

Sharpless

by addition

(in a 2:l ratio)

of

[Ti(OPri)4/

cleanly

sulfoxides

[408]. Use of TiC12(0Pri)2

(+)-diethyltartrate

Referencesp.435

2S,3S-Epoxygeraniol

excess

to give a new homogeneous

/H20/tBu00H

polystyrene

were used in the epoxidation

with up to 66% enantiomeric

for asymmetric

1 mol equiv. dizes

esters

via -CH2OH or -CH2CH2OH

instead affords

oxi-

with

of Ti(OPri)4 the chloro

406

diols

(172) arising

from regiospecific

epoxides

of opposite

analogous

standard

opening

enantioselectivity

asymmetric

of intermediate

to those produced

epoxidation: /Cl OH OH JG

t &OOH “-C14H29 &OH

Similar

TiC12(OPri)2

"inverse"

tions catalyzed

l

epoxides

by Ti(OPri)4

(I.7411 in the 2:l ratio

DET

c

n-W-&

(173) are also obtained

and tartramide

Bu OOH

OH

figands

172

in oxida-

[for example

[409].

t Fh

in the

Ti fOPri)4

Ph

>

+ (174)

OH

Ph 173

NHCH2Ph

t.K).-*

Asymmetric Ti(OPri)4,

epoxidation

(+)- or

(-I-diethyl

products

with

opposite

to that observed

-characterized

of homoallylic

23-558 optical oxotitanium

epoxidation

of cyclohexene

alkylperoxo

complex

lytic cycle

L4111.

tartrate,

yields.

for allylic complex

alcohols and tBuOOH

the

system

affords

The enantiofacial selection alcohols [4101. The well-

(TPP)Ti=O

with tBuOOH

(175) is proposed

using

is a catalyst

for the

at 70°C. The cis-hydroxo to be involved

175

is

in the cata-

Epoxidation in benzene

afforded

same epoxidation three epoxides The oxidation metal

lective

(5S)-5,6-epoxyvitamin

and the reaction

of the triangular heterolytic

the coordinated

The

in a mixture

needed reflux temperature heterolytic

peroxide moiety.

epoxidation

comprises

Homolytic

olefin.

resulted

by H202 and ROOH catalyzed

(176), involves

e.g.

by VO(acac)2

D3 in 90% yield.

as catalyst

with MOM

of hydrocarbons

peroxides,

cleavage

D3 with tBuOOH catalyzed

of vitamin

[4121. with do

or homolytic

The mechanism

of se-

the peroxymetalation

epoxidations

of

of

are less selective

[4131.

176

Cyclohexene MO(V)-TPP

was epoxidized

complexes

(hexene, isoprene)

of alkenes

was obtained

carried

than with MOM

ligand

EDTA,and

oxalate,

of

In the epoxidation

higher rates of cis vs. trans isomer

with Mo(TPP)(=O)X

control of the macrocyclic molybdenum

with tBuOOH in the presence

with up to 84% selectivity.

due to the steric

[414]. The catalytic

phenoxy

complexes

activity

of

in epoxidations

out with tBuOOH varied with the ligand used. The complex

containing

phenoxy

investigated catalyzed

ligands was the most active

[415]. Epoxidation

by cetylpyridinium

of allylic

in the reaction

alcohols

12-molybdatophosphate.

of geraniol

proceeds

Epoxidation

of sardine oil by cumene hydroperoxide

with H202 is The epoxidation

with high regio- and stereoselectivity

of MO acetylacetonate

as catalyst

Epoxidation

of olefins

conversions

and selectivities

with Co or Mn stearate

is best performed

with cumyl hydroperoxide were obtained

like tBuOOH or PhCMe200H

by Mo02(acac)2

at 116OC

was studied.

with Mo2B5

[4181. The decomposition

[4161.

in the presence [4171. Best

combined

of hydroperoxides

and similar Mo(V1)

complex-

es is a molecular and not a free radical mechanism. The significance of this decomposition reaction in the MO-catalyzed epoxidation of olefins was discussed epoxidation butene

of cyclopentene,

[4l9]. Kinetics cyclohexene,

and of styrene with hydroperoxide

and V02+ immobilized vinylbenzene

References p.435

on a chloromethylated

were determined

[ 4201.

and selectivity

cyclooctene,

of

2-methyl-22+ of Moo2

in the presence copolymer

of styrene

+ di-

408 Hi-, ei-

and tetrasubstituted

olefins may be epoxidized

with

high yields using NaCCl as oxygen Source and Mn(TPP)CSicas catalyst in the presence of pyridine. Kpoxidation is stereospecific with s addition of the oxygen atom [421]. The catalytic epoxidation of terminal

olefins

reasonable

with NaOCl and Mn(TPP)OAc

yields because

lyst competes

the oxidative

with the epoxidation

is not possible

decomposition

of the poorlyreactive

It has now been found

that using modified

containing

Ph groups like C6F5 or o-F-C6Hq,

substituted

yields of epoxides may be obtained substituted cis-stilbene

pyridines

dinate

to the metal.

Mn(TPP)(=O)L+Clcharacter

increased

oxygen

[423]. The effect of pyridine

olefin

epoxidation

mining

by NaOCl catalyzed 14241. Kinetic

step in the epoxidation

NaOCl is the conversion (VI-species increases inactive catalyzed

the porphin addition

of pyridine

a more concerted

of

transfer

on the stereoselectivity by Mn(III)-porphyrin

of of

complex-

by Mn(TPP)OAc

and

into an oxo-manganese

of the porphyrin by preventing of a-stilbene

and the Mn(porphin)Cl

to a support

the formation

of

by NaOCl was

complexes

containing

(177) or (178). In the case of Mn(TPP)OAc significantly

changed

the &:franq

ratio but no such effect was noted with the catalysts ligands

coor-

py) with a more oxenoid

of a Mn(III)-species

[425]. Epoxidation

ligands

of

data suggest that the rate deter-

(TPP)Mn=O. Anchoring

by Mn(TPPfOAc

strongly

to the formation

of cyclohexene

the rate of epoxidation dimers

20-80%

system has been investigated.

(L = substituted

of the Mn=O group ensuring

es was discussed

ligands

of epoxidation

with ligands which

This was attributed

complexes

olefin.

[422]. The effect of various

on the stereoselectivity

with the NaOCl/Mn(TPP)OAc

The stereoselectivity

porphyrine

with

of the cata-

(177) or (178). This proves that pyridine

(axial) ligand in the TPP-systems

epoxide containing

acts as the fifth

[426].

R + R = -CsHeO(CH2,120CsH4-

177

409

In the presence

of imidazole,

lyze the decomposition a high-vale& dation

epoxidizes OCN-).

0x0 complex

takes place

cyclohexene

is formed.

accept

O=Mn(TPP)(X)

epoxide.

The rate constants

which

ly stable Mn-oxo metal

of olefins

of Mn(TPP)X

depend

transfer

to cyclohexene

from the olefin

porphyrin

stilbene

of olefins properties

epoxidation

Mn porphyrins

Oxidation

are remarkably

with

tBuOOH.

of styrene

and stilbene

becomes

olefins

of Pd(OAcj2.

olefins.

Pi?

tBuMepSiOCOOCPh

Referencesp.435

yield

of bpy. The method

/d-

and with

is espe-

olefins

exclusively

Ph

Ph p

+

(179)

of a catalytic

are inert under

trans

products

[433].

peroxybenzoate

in the presence

are the main

ph

occurs

silyloxyalkyl

Ph

+

autoxidation

with FeC13

It is s~f! and stereospecific

Electron-deficient

cis epoxides

in the

is the main

by NaI04 was effected

and no isomerization

into epoxides

studied

Epoxidation

reaction

in the presence

conditions., Trans olefins

179

(32%) was achieved

If O2 is present,

of olefins

The cyclopropyl-substituted

A

yield

for the epoxida-

by PhIO was

the predominant

suited.:for internal

cis olefins

and

to those of the Fe and

and Fe(TPP)Cl.

[4321. Epoxidation

transforms

similar

Highest

with all three catalysts.

for both E and 2 alkenes

amount

[4291. Soluble

epoxidation

were used as catalysts

.FeC13, Fe(acac)3

RuC13. nH20 as catalyst cially

and a high-valent

and epoxide

14311.

to benzaldehyde Fe(acac13

of a relative-

and of cumene by iodosylbenzene in MeCN. of the Fe and Mn salts with regard to

compounds

tion of cyclohexene with Tc~(CO)~~

reaction

is very large

[430].

Technetium

presence,of

the

upon

porphyrin-catalyzed

is the decomposition

ion salts of Mn, Fe, Co and Cu catalyze

hydroxylation The catalytic

as "oxene" to to yield

formed

to Mn(II1)

(X = halide,

for this oxene

step in the Mn(II1)

epoxi-

N-oxide

reacts with cyclohexene

by LiOCl

intermediate

complex

probably

are present,

the 0 of the N-oxide

X, the rate of 0 transfer

[428]. The rate-determining

cata-

Transiently

If olefins

in the presence

generate

epoxidation

and Fe(TPP)Cl

[427]. p-Cyano-N,N-dimethylaniline

The Mn complexes

the ligand

Mn(TPP)Cl

of cumyl hydroperoxyde.

epoxides,

[434].

9 + t BuMqSiOCPh

0

C-Ma

the

from

410

The complex terminal

(dppe)Pt(CF3)(0H)

alkenes

of the system. Olefins

The selectivity

of the reaction

are much

lower and an induction

isomers

See also

[385, 394, 395, 401, 4751.

give trans-stilbene

Oxidation

ZrOtOAc)2

of O-containing

catalyzes

hols with

tBuOOH

formation

of carboxylic

carbonyl

of secondary aldehydes

Olefinic

double

alcohols

affected

and primary

are chemoselective, The alcohol

es like MO02(aCaC)2 the single

bond between

oxidizes

acids with

of

secondary acids.

to olefin

shorter

into alco-

of MO complexcarbon

at the double

and the allylic

The

epoxidation

14401. Allylic

in the presence

the olefinic

tBuOOH.

are not transformed

regioselectively

cata-

primary

with

to carboxylic

carbonate

tBuOOH

[4381.

to ketones,

in preference

to carboxylic

is cleaved

ion

cata-

is a selective

peroxide

alcohols

of potassium

with excess

to the

The recovered

[4391. In the presence

olefins

oxidation

stems from the presence

The molecule

of alcohols

into

on

supported

to acids or esters

fNH4)6M07024. 4H20 and R2C03, hydrogen to ketones

are converted

loss of the Cr(II1)

to esters,and

arenot

Both

alco-

of primary

alcohols

with tBuOOH.

lyst fox the oxidation

hols axe oxidized

oxidation

tetrabromooxomolybdate

bonds

is observed.

Groups

the oxidation

compounds

alcohols

epoxides.

99% 14351.

[4361.

[4371. Chromium(II1)

lyst could be reused without

oxidations

period

Functional

acids. Allylic

aldehydes

Benz~ltr~ethy~~oni~

alcohols

is over

with very good yields without

511 was used to catalyze

corresponding

oxide

the selective

into aldehydes

a, p-unsaturated Nafion

of

requirement

by iodosylbenzene in the presence + ions are used, as solvent. If Cu

stilbene

C)

the epoxidation

is an essential

can be epoxidized

of cu2+ ions in acetonitrile the yields

catalyzes

35% H202. Wates

with

chains.

bond and at

carbon

atoms

[4411:

ToH The oxidation reagent)

produces

distribution

of mandelic benzaldehyde

studies

(4421. Oxidation

b

suggest

C00H

C

acid by Fe(II)

-“\COOH

+ Ii202 (Fenton's

and phenylqlyoxylic an Fe(W)

of dihydroxyfumaric

species

+ HCOOH

acid.

Product

as intermediate

acid by H202

in the presence

411 of Fe2+ as catalyst

is first order

[4431. The Fe complex III

adsorbed

of ascorbate

at an octane/water

termining

hexacyanoferrate(II1)

1x(111)-catalyzed determined

oxidation

tuted benzoic and Ru(II1) -catalyzed

oxidation

of cyclopentanol, in aqueous

sulfuric

alkalic,

medium

between ments

alkaline dride of

proceeds

Ru(VIj and the substrate

a mechanism

is supposed

a-hydroxyesters

by a large number on carbon

and

is a useful

Ru

R-CB-z+t3uoH

Ru(II)-,and

-

R-c-z

Ph, 2-furyl, COOEt,

The Ru(I1) photo-oxidation

Referencesp.435

of traces experi-

of dials by

by RuO4. A Ru(VIII)

hy-

[451]. Dehydrogenation

by tBuOOH

is catalyzed

Ru(III)-compounds.

Even Ru

+ H20 -I- tBl.loB

II

OH

2 = COOMe,

in mild

[452]:

I

R = Me,

was

of a complex

for the oxidation

u -hydroxynitriles

catalyst

by Fe(CN)i+

[45Oj. Based on kinetic

as an intermediate

of Ru(Ofr,

hydride

in the presence

catalyzed

sulfate

for the oxidation

via the formation

has been suggested

hexacyanoferrate(III)

species

ketones

were determined

The oxidation

to

and zero

by Ce(IV)

A Ru(II1)

14491. Rate constants

to the corresponding

aqueous

iodosoacetate

[448]. The RuCl3-catalyzed oxidation

of cycloalkanols of Ru(V1).

each in Idi

to nxidant

and cycloheptanol

acid was investigated.

as an intermediate

substi-

[4471. The Ru(III)-

by phenyl

to substrate cyclohexanol

were

of aryl styryl

is first order

in substrate

of 1,3- -1

from and

iodosoacetate

oxidation

is first order with respect

order with respect

abstraction

to the corresponding

acids

order

acid

The rate de(3-x)+

of the Ru(III)-

of iPrCX$by phenyl

and phenylacetic

3-hydroxybutanal

proposed

by hydride

and mechanism

in acid medium

and fractional

[4441. The ki.net+

phase

of OH- from Ru(H~O)~_~(OH)~

[446]. The Ru(III)-catalyzed

by periodate

the oxidation

by 2-N-methylamino-1,4-

has been examined.

and this is followed

[4451. Kinetics

and oxidant

of lactic acid and acrylic

step is the displacement

the substrate

ketones

oxidation

catalyzes

phase)

dissolved--in the organic

by the substrate

, substrate

ester of coproporphyrin

interface

in the water

its of Ru(III)-catalyzed by alkaline

2+

of the tetramethyl

(dissolved

-naphthoquinone

in Fe

2-thienyl,

(E)- PhCH=CH

CN

polypyridyl

complex

RuLy

of benzylic

alcohols

to aldehydes

(L = 180) Eatalyzes by visible

the

light

412 in the presence The diazonium fluorenone

of a diazonium

salt

salt is concomitantly

(181) as quencher reduced

and a base.

to benzophenone

and

[4531.

COOPr

i

COOPr i 180 Oxidation NaI04

181

of the benzofurane

in the presence

Using 02/PdC12/CuC1 obtained

derivative

of 0~04 afforded

catalytic

(182) (khellin)

the hydroxyaldehyde

oxidation

the hydroxyester

by

(183). (184) was

14541.

183

OMa 0

Ma

182

Ma

184

Oxygen

inhibited

of acetaldehyde Alcohols following

R\

secondary

reactions

of AcOOH

in the oxidation

in the presence

may be oxidized

sequence

HR7C -OH

of Co 2+ ions [4551. to aldehydes or ketones

of reactions

PO

+ CIC\o_

Pd (OAc)2 80 ‘C

C

R\ R,’

using

the

[456):

/O

R\

-

H-+c-o-c\o_

c=o

+

CO2

+

C3Hfj

-

413 Pt complexes in the presence

catalyze

of water

The oxidation reaction

of ascorbic

solution

suggests

by 12

are present

like PtXi- or PtXi-

[4571.

acid by tris(oxalato)cobaltate(III)

is catalyzed

a mechanism

alcohols

acids which

Pt halide complexes

(X = Cl, Br, I) were the most active in aqueous

of primary

to give carboxylic

Unsubstituted

as esters.

the oxidation

by Cu(I1).

involving

The rate law of the

a copper-ascorbate

complex

[4581. See also d)

[469, 5311. Oxidation

Tungstate nitrones

of N-containing

catalyzes

Organic Compounds

the oxidation

of secondary

I

-c-NHI H

I+ -C+NI d

Na2yx)4 _ 4

+ H202

Other catalysts are somewhat

such as VO(acac)2,

less effective

The hydroxylation The highest

Ti(OBu)4

of acetanilide

(6.7%) was obtained

systems

using catechol

of (TPP)FeCl and

oxygenases strength order

by potassium

are first order

in p-RC6H4NHAc

reaction

if

4-aminobutyric investigated. volves

P450 dependent

of the Ru(III)-catalyzed

These mono-

oxidation

(R = H, Me, Cl, N02). The products

of

hexacyanoferrate(II1)

to kinetic measurements

of a Ru(III)-substrate

poses to a Ru(II1) hydride

and succinic

ing step

14631. Oxidation

Fe(CN)i-

with RuC13 as catalyst

of the

if R = H and the corresponding

R # H [462]. The Ru(III)-catalyzed

According

Referencesp.435

[4601. Oxida-

and tBuOOH in the

iodate in aqueous AcOH at constant ionic 3+ in Ru , zero order in HI03,and complex

acid by alkaline

the formation

catechols.

(TPP)MnCl gave PhCHO and PhCH20H.

are o- and e-benzoquinone

o-benzoquinones

substituted

with 3,5-di-tBu-catechol

for the cytochrome

[461]. Kinetics

acetanilides

+ Fe (III) +

(o-,m-,and E-) acetamido-

by PhIO, 3-C1C6H4C(0)OOH,

served as models

and MoOa (acac12

[459].

yield of the three isomeric

tion of (PhCH2)2NN0 presence

to

(40-89%)

H202 systems has been studied using different phenols

amines

by H202:

of isoleucine

oxidation

of

ions was

the mechanism

in-

complex which decom-

acid in the rate determinand glutamic

acid by

was found to be first order in

414 catalyst

and zero order

ion transfer

from the amino acid

[464]. Nicotine presence

in oxidant.

was oxidized

of Ru02

A mechanism

c-carbon

involving

to Ru(II1)

to the lactame

hydride

was proposed

(185) by NaI04

in the

[465].

185

Amino

acids were oxidized

in the presence formation

of Os(VII1)

of a transient

to aldehydes

catalyst.

by alkaline

The reaction

amino acid complex

with

[Fe(CN)613-

proceeds

through

[OSO~(OH)~]~-

[466]. A free radical mechanism was proposed for the oxidation of 2by S208 catalyzed by Cu2+. The reaction was first order

glycine oxidant

and zero order

tion of tBuNHNH2 presence

Cu(I1) was determined.

complex

between

products

are N2 and tBuOH

See also

14691.

e)

[4671. The kinetics

Oxidation

Cu(I1)

in the

The reaction

and the substrate.

in

of oxida-

by tris(dimethylglyoximato)nickelate(IV)

of aqueous

intermediate

in substrate

involves

an

Oxidation

[468].

of P-, S- or Halogen-containing

Organic

Compounds Iron(induced

oxidations

drous

acetonitrile.

place

if H202 is slowly added

the organic zobenzene,

for the systd strate

(olefins,

by the Ni(I1)

[470]. A modified

diethyl

alcohols,

;f Fe2+ is added

tartrate

containing

aldehydes,

Dioxygenations to a solution

of tBuOOH

in anhy-

reagent

Fe

take 2+ and

ketones,

hydrit

are characteristic

of H202 and the sub-

by triphenyl

salt of 0,0-diisopropyl Sharpless

studied

and dehydrogenations

to a solution

PhI,sulfoxides).

(4691. The reduction

catalyzed acid

Monooxygenations

substrate Ph P

with H202 were

composed

+ H20 + 2 tBuOOH homogeneously

phosphite

is

dithiophosphoric of Ti(OPri)4 oxidized

+ 2

sulfides

to sulfoxides. highest

The optical yields ranged from 4 to 93% with the being observed in the case of methyl p-tolyl sulfoxide [4711.

Organic

sulfides,

sulfoxides

dissolved

with aqueous

in nitronethane,

nitric

may be oxidized

acid in the presence

to

of Bu4N+AuCli

43.5 as oxidation thio group contains etc.

tungstate catalysts

was found

zero order

epichlorohydrin. with

alcohol

The most tBuOOH

Stoichiometric

were deter-

catalyzed

Oxidation

ketones,

by

ing phenols

of Hydrocarbons peroxides

high concentration

to

abietate,

prepared

a

from

with Hiqh Vafent

like

or Hydrocarbon

Groups

(tBuO)2MOOBut

[M = Al,VO]

to the corresponding to 1,2-epoxyoctane

secondary

of succinic

or sec. octenols,

Bu20

to the correspond-

25OC gave 91% cholest-5-ene-3-one

acid by chromic

[4771. Oxidation in CH2C12

(186) (R = H, MeO)

+ HC104

CaC03

14791,

186

at

of l-aryl-l-pro-

-f MeCN gave the

0

OMa

in

of choles-

containing

[478]. Oxidation

penes with Cr03 + HBF4 + MeCN or Cr03

acid at

acid were first order

in substrate

chlorochromate

R

oxi-

alcohols

[476].

of perchloric

and second order

Referencesp. 435

in sub-

tested as

with tBuOOH

Compounds

and PhMe, PhOMe and mesitylene

terol with pyridinium

were

were molybdenum

of Organic

of the oxidation

I-aryltetralones

and first order

MO compounds

efficient

in > 99% yield

Kinetics

in oxidant

by sodium

Complexes

1-octene

to PrCHO acetals,

with H202 catalyzed

of ally1 chloride

Oxidation

Metal

Organometallic

oxidant

hydroxy,

[475].

dize C5 - Cl0 n-alkanes

very

parameters

and EtOH, and a compound

and Moo3

Transition

and/or

amino,

by chloramine-T

[474]. Several

for the epoxidation

MO complex

a)

and activation

of ally1 chloride

strate and catalyst

decyl

out also if the molecule

such as tertiary

of MePhSO

of the

[4731.

Oxidation

6.

groups

for the oxidation

Os{VIII)

The oxidation

and may be carried

is selective

other oxidizable

[472]. Rate constants

mined

catalyst.

and phase-transfer

416 Oxidation

of

(187) with the Cr03 + HBF4 + MeCN

reagent

gave

(188) [4801.

OMe

OMe Me0

Me0

L

Me0

0

188

187

Phenyl K2Cr207 tally:

alkyl ketones

or KMn04 to yield

were photo-irradiated 1,4-dicarbonyl

Phi,, ) R 23

Treatment

of 2-octanone

gen transfer

(epoxide)

Substituted Methyl

[481]. Reaction

biphenylenes

substituents

regiospecifi-

a mixture

of ClCrOg with

ions deriving

and from cleavage carbene)

of

P P PhaX2CH2CR

-

ion flow tube gives product

hyde and a Cr(VI)-oxo

compounds

in the same way afforded

2,6- and 2,7-octadiones a selected

in the presence

of 2,5-

ethene

in

both from oxy-

of the alkene

(formalde-

[4821. were oxidized

were oxidized

in AcOH with Mn(OAc)3.

to formyl and acetoxymethyl

groups, the oxidation of other derivatives yielded nuclear acetoxymethylated products [483]. The oxidation of CL, P-unsaturated ketones ones

with Mn(OAc13

in refluxing

(189) in good yields

benzene

furnishes

[484].

0

0 AcO

189

c'-acetoxyene-

Oxidation

of dialkyl malonates

Michaelis-Menten

type kinetics

cetyltrimethylammonium corresponding

cis-dihydroxy

the formation MnOi

in good yields.

and the oxidant

PhCOCOPh was

[486]. The oxi-

to both acetate and MnOi

formed by the reaction

of KMnO 4 with cyclohexene

hydrolyzed

of alkenes with

by MnOi in alkaline and neutral media

was first order with respect of cis-1,2-cyclohexanediol

in

with a

in CH2C12 at ZOO gave the

compounds

of PhC rCPh

dation of NaOAc to oxalate

84% with stirring

pyrophosphate

14851. Treatment

permanganate

formed in the reaction

solution

by manganic

The results were consistent

aqueous AcOH was studied.

efficiency

increased

and dilution.

of an intermediate

[4871. Yields

of a MeOH/water

from nearly

zero to

This was attributed

hypomanganate

ester which

by water to glycol but is further oxidized

to

is

by excess

[488]. Phenanthrene

90% aqueous a radical

is hydroxylated

cation intermediate

Fe(CN)z-

at the g-position

acetic acid. The oxidation

giving aldehydes

substrate,

oxidant,

(4891. Oxidation

as major

products

and acid. A radical

intermediate

[4901. The peroxo complex

alkanes

only in the presence

(Ac20). The active to the following

species

of xylenes

in

of

by acidic

is first order each in

by ESR spectroscopy to alcohols

by Fe(CN)z-

proceeds via formation

was detected

[Fe(TPP)021-

of an acylating

is [F~(TPP)o]+ which

oxidizes

agent

is formed according

stoichiometry:

Ac2O

-

[ (T=%J21-

-AC!O(TPP)F&XJAc -.(Fe(TPP)Ol+

-AcO-

This chemical P-450

system is at present the best model of cytochrome

[491]. Oxidation

of cyclohexene

+ Ac20 and Fe(TPP)Cl

Fe(TPP)02

cyclohexenol-1

and cyclohexene

hexene oxide is formed. Fe(TPP)Cl

The peroxo complex yields

oxide ; with the peracid only cyclo-

The oxidation

of cyclohexane

+ (RCO)20 system is independent

anhydride.

The oxoferrylporphyrine

responsible sulfuric

was studied using the systems

+ AcOOH.

for these oxidations

acid containing

benzene

of the nature of the

cation radical

[Fe(TPP)(O)l+

[492]. When aqueous and iron(II1)

formation

increased

in weakly

References ~435

solutions

is of

sulfate were irradi-

ated, low but reproducible higher

with the

amounts of phenol were obtained. Phenol 3+ with increasing Fe concentration and was

acidic

(pH k 3.5) solutions

[4931.

418 The kinetics of oxidation and perruthenate

of trans-cinnamic

ions was studied

ethers were subjected

14941. Allylic

to oxidation

Oxidation

of various

alcohols and their

by 0~0~. The main product had

in all cases erythro configuration OH or OR group and the adjacent

acid by ruthenate

with respect to the preexisting

new OH group

aryl-conjugated

14951.

olefins

like styrene with

Co(OAc)3

in wet AcOH under N2 gives the corresponding

acetates

in good yield

phenylethane

[4961. Cobalt(II1)

glycol mono-

acetate oxidizes

in acetic acid to the side-chain

substituted

1,2-diproduct

(190):

-

PhcH2cH2m

PhCMe201e2P

=2ph I

191 190

No reaction

occurs in the case of (191) indicating

acetoxylation

starts with H atom abstraction

that side-chain

from the

a-position

[4971. Alkenes catalytically

are stoichiometrically, oxidized

and in the presence of air,

by (MeCN)2Pd(N02)C1.

ture of the olefin, ketones, ketones,or

epoxides

lectivity.

Heterometallacyclopentane

complexes

(192) are

192

Pd

[388]. Epoxidation

Stoichiometric

of Olefins epoxidation

of (193) to form disparlure

was carried out with MoO5L complexes. succinate

of type

[498].

L “r I/‘\ 0-N’ ‘Cl’ k+:, b)

on the struc-

Ct,p -unsaturated

are being formed, in some cases with good se-

formed as intermediates

See also

Depending

ally1 alcohols,

If

(194)

L = Me2(-)-2-piperidino

57% yield of (+)-(194), if L = Me2(-)-2-morpholinosucci-

nate 39-46% yield of c-)-(194) was obtained

[4991.

419

The interaction clohexene

formed by excess of MO complex dation

is performed

oxygen

ligand

probably

transfer

stoichiometric containing

epoxide which

into 1,2-dibromocyclohexene.

by a MO peroxo

epoxidized

reaction

(S)-dimethyl

with

complex,

to (196) with

a Mo(VI)-oxodiperoxo

lactamide

q+Jy

with

cy-

is then transEpoxi-

formed by di-

from Ni [500]. The tetracyclic

was enantioselectively

teucoo

and Mo02Br2(0PPh3)2

of (tBuNCj2Ni02

leads first to cyclohexene

olefin

(195)

53% o.y. using complex

the

(197)

[501].

(197)c

OoCEd

0

tBu 196

195

MqN-

197

I: OH 1 /H

C -C

he The

"oxo-like"

Mn porphyrin

= tetramesitylporphyrinato) stoichiometrically OPPh3,

oxidizes

respectively.

styrene See also c)

with

NaOCl

(TMP =

from Mn(TMP)Cl

and NaOCl,

and PPh3 to styrene

is also an effective

under phase

transfer

oxide and

catalyst

conditions

for [x)2].

[498, 4821. Oxidation

The kinetics in acidic

styrene

The complex

epoxidation

complex Mn(TMP)(O)Cl

obtained

of O-containing of oxidation

solutions

Functional

of diethylene

was examined.

A radical

15061. The rate law for the oxidation

Referencesp.435

Groups glycol by vanadium(V)

mechanism

was proposed

of 2-ethyl-1,3-hexanediol

by

420 vanadium(V)

in water-dioxane

in H +,and

-order

oxidation diedin

first-order

glycolic

acid were

acidclactic

further

oxidation

D-galactose, in diluted H2S04

in aqueous of PhCHO

D-xylose,and H2S04

are oxidized

chromate

useful

The kinetics chromate

were

energies,and collagen mate

oxidation

studied entropies

were oxidized

[5111. Oxidation

of partially

of several

in DMSO.

were determined to carbonyl

at room temperature

followed

oxidant,and

or ketones

or allylic

is

alcohols

acetyl.ated aldohexo-

effects,

by pyridinium

[5091. chloro-

activation in

chlorochro-

(198) by pyridinium

by treatment

furnished

and

chloro-

[510]. The OH groups

alcohol

of

peroxydichromate

chlorochromate

isotope

groups

of the ally1

in CH2C12

system prevented

dials with pyridinium

Kinetic

[505].

The new reagent

of benzylic

out with pyridinium

of oxidation

chlorochromate -MeOH

at room temperature.

was carried

acid

by tetrabutyl~onium

for the oxidation

[508]. Regioselective piranosides

to aldehydes

stu-

in the

15061. The oxidation by chromium

of

by chromic

system

each in substrate,

are oxidized

were

and in a two-phase

L-arabinose

to disulfides

(Bu4N)(Cr03Clf

especially

alcohol

The two-phase

to the acid

is first order

[5071. Alcohols

thiols

of benzyl

solution agent.

5+ ,third-

increased

acidctartaric

acidcmalic

a phase-transfer

in V

[504]. The kinetics

The reactivity

rates of oxidation

similar

containing

first-order

acids with vanadium(V)

acid solutions.

The reaction

was

in substrate

of 2-hydroxycarboxylic

perchloric

order

medium

with Mn02/NaCN/AcOH

the ester (199) in 75% yield

[5121.

199

198 Pyridinium aI p-unsaturated [5131.

chlorochromate 6-lactones

0 0

200

oxidizes

5,6_dihydropyrans

(201) with good to excellent

n 0

201

0

(200) to yields

421 Selective primary

oxidation

of secondary

ones has been achieved

by

alcohols

(a) protection

hols by tBuMe2SiC1,

(b) oxidation

nium fluorochromate

or benzyltrimethylammonium

(c) deprotection hols

(benzyl,

rochromate

of primary

ethyl,

of secondary

hydroxyls

cyclohexyl)

in the presence of primary

alcohols

independent

of substrate

chlorochromate,

in MeCN/PhN02

derivative

concentration

dichromate

by pyridinium

useful

fluo-

to oxidant

[515]. Oxidation

is generally

and

of alco-

of

and Ac20 gave the corresponding

(203). The method

of alcohols

alco-

by pyridi-

[514]. The oxidation

was found to be first order with respect

with pyridinium

of

and

(202) carbonyl

for the oxidation

[516].

0-a-l-J Ph

<(a R

OMe

R’

The induced Cr(V1)

+ Fe(I1)

transfer

involves

of oxalic

has an inhibitory prepared

tion

that Mn(II1)

oxidation aqueous

behavior enhances

of mandelic

AcOH or aqueous against

photometrically.

effect on the reaction and phosphoric

rate

decreased

oxidation The most

cyclohexanol

[520]. The kinetics

the reactive

oxidizing

for the oxidation of ribose

by‘KMn04

aldehyde

with

tive reagent

agent. An acyclic dials

in the presence

permanganate

for the oxidation

Referencesp.435

propororganic

spectro-

mesityl

and

of dials and

mechanism

was proposed of oxidation

of acid was determined of the oxidation

by flow injection

[5221.

of benzanalysis

was found to be a highly

of benzylic

oxide

HMnO4 was found to be

[521]. The kinetics

rate constant

KMn04 was determined

Cetyltrimethylammonium

studied.

in

cyclohexanone

of the oxidation

MnOq were

of vicinal

The pseudo-first-order

increasing of different

active were p-benzoquinone,

the least active were caprolactam, by acidic

conducted

by KMn04 has been determined

and aniline,

their monoethers

by the observa-

[518]. The rate of

with

[519]. The reactivity

[5171.

acid oxidize

The reaction

can be explained

the reaction

dioxane,

by

the acid to CO2 via

and acetaldehyde.

which

monoanion

of Cr(V) by one-electron

acid by Mn(III)pyrophosphate,

tions of AcOH or dioxane compounds

acid or oxalate

from MnO(OH)2

to formaldehyde

shows autocatalytic

RR’ = 0

the formation

'ooccoo-. Mn(I1) propane-1,2-diol

203;

Cr(V) then oxidizes

Mn(IV)

solutions

R = OH, R’=H

OTs

oxidation

from Fe(I1);

202;

alcohols

[523!. selec-

to the corre-

422 sponding

aldehydes

chloromethane by Fe

Oxidation

or ketones.

solution

was carried out in di-

at 30°C and yields were 90-98%

[5241.

Kinetic parameters for the oxidation of pentoses and hexoses 3+ in H2S04 at lOO-130°C were determined [525].Monosaccharides

were oxidatively

degraded

to monosaccharides

by FeCl3 under irradiation

with near-UV

with less carbon atons

to visible

degradations

were shown to proceed via formation

nosaccharide

complex

with Fe(CN)z-

[526]. Oxidation

diamine

of D-galactose

follows

via a radical-anion by Fe(CN)%-

zero order kinetics

first order both with respect of enolization coupling

phosphate

of phenols

mechanism

in the presence with respect

the oxidation

and

15271. The

of ethylene-

to Fe(CN)z-

to sugar and OH-. Probably

is rate determining

alkalic Fe(CN)zoxidant

of glyceraldehyde

at pH 8-11.5 was first order in the substrate

gave =02P(0)OCH2CH(OH)CO; oxidation

light. The

of an Fe(III)-mo-

and

the rate

[5281. In a study of oxidative of resorcinol

and orcinol with

was found to be first order each in substrate,

and alkali. A radical

2-(Vinyloxy)phenols the corresponding

intermediate

(204) were oxidized quinones

was observed

[5291.

by FeC13 or K3Fe(CN16

to

(205) and with AgO or Ag20 to the dimers

(206) [5301.

204

206

R=MeO-;

0x0 complexes nic compounds. carboxylic

CHO R

OUN-

of Ru(V1) and Ru(VI1) were used to oxidize

Thus RuOi- and RuOi

acids and secondary

and Ru02(bpy)C12

cleanly

hydes and ketones without lyses the oxidation

oxidize

alcohols

oxidize

primary

to ketones.

alcohols

orgato

(Ph4P)(Ru02C13)

to aldeattack on the double bond. RuOz- cata-

of alcohols

a wide range of alcohols

by S20i-

[5311. Ruthenium

dioxide

423

hydrate

oxidizes

allylic

and also effectively oxidant

catalyzes

transformed

of olefin

to unsaturated

carbonyl

the same oxidation

at 70° in dichloroethane

with retention hyde

alcohols

as solvent.

stereochemistry,

into citral consisting

compounds

with air as an

3he oxidation

thus geraniol

proceeds

(207) is

of 97.5% of the E-isomer

alde-

(208) 15321.

207

208

The rate of L-ascorbic acid oxidation order with respect The kinetics

to both the substrate

of oxidation

benzaldehydes

of benzaldehyde

by Na21rC16.6H20

isotope effect

indicates

and some substituted

were studied.

that the cleavage

bond is the rate-determining of ascorbic

by Co(NH3)z+ is first and the oxidant [5331.

step

The large deuterium

of the aldehydic

[5341. The kinetics

acid by triscdimethyl-glyoximato)nickelate(IV)

investigated.

The reaction

nism involves

a rate-determining

C-H

of oxidation was

is of pseudo first order and the mechaouter-sphere

one-electron

transfer

[5351. Rate constants

and activation parameters were determined for of furfural by Cu 2+ , Fe3+, Ce4+, Ag+, Hgz' and Hg2+.

the oxidation A one-electron cations

mechanism

was proposed

and a two-electron

The kinetics

of oxidation

mechanism

of dihydroxyfumaric

nit acid by Cu2+ was studied were oxidized kinetic

step is the one-electron dative coupling ethylamine-Cu(I1) phenanthryl 15391.

References p. 435

in aqueous

leads to the conclusion reduction

of 9-phenanthrol complex yielded

[5361.

acid to diketosucci-

[537]. Butanone-2-

by K5[Cu(H2Te06)2]

evidence

for the first three of these for the other cations

and cyclohexanone

alkaline medium.

The

that the rate-limiting

of Cu(II1)

to Cu(I1)

[5381. Oxi-

(209) with a (-)-(R)-1,2-diphenyl(-)-(S)-lO,lO'-dihydroxy-9,9'-bi-

(210) in 86% preparative

yield and 98% optical

purity

424

\

‘y \

-

210

8 209 See

also

[30,

4051.

Oxidation

d)

of N-containing

The stereoselective with peroxomolybdate -oxides tively

(2lla) and

oxidation

Organic Compounds of l-benzylnicotinium

and peroxotungstate

(211b) in the ratio of 14:l and 15:1, respec-

[5401.

P hiH2

PhtHp

211b

211a

Based on kinetic measurements, the oxidation

of leucine by manganic

The kinetics

of the oxidation

concentrated

sulfuric

acid catalyzed.

was proposed

oxidation

for both reactions

prepared

by refluxing

reaction

The oxidation

[5421. Colloidal

is

Mn02

a homogeneous

take place. Mechanisms

solution

[5411.

of Me2NH by acting as a

[5431. 2,2'-Binicotinic

the water

for

by KMnO4 in moderately

Due to this simultaneously

proposed

[544].

was proposed

sulfate in acidic medium

of L-arginine

in the MnOi oxidation

catalyst.

and a heterogeneous

a mechanism

acid has been determined.

A mechanism

species participate heterogeneous

KMn04

bromide

gave cis- and trans-l'-N-

acid

were

(212) was

of phen with NaOH and

425

An isotopic of oxonitine

/\ d-b -bJ

/\

212

N--

labeling

study has shown that the N-formyl of XMnO4 oxidation

from the methylene

group

group

of aconitine

of the N-ethyl

of aco-

[5451.

Oxidation FeL(OH)z

of L-adrenaline

ions

-determining

transfer

electron-transfer compound,

of electron

in some cases

R = CH2CH3

in the presence

derivative

was studied.

from the substrate stereoselectively

donor

acted as a one-electron

in the presence

[547]. The oxidation

(R, R = H, Me) with FeC13

gave pyrimido

215

of

to The rate-

to the central [5461. The

donor

a NADH in MeCN. in the

of a base it acted as a of 5,6-diaminouracil pteridinetetrones

[548].

Referencesp.435

bound

from I-benzyl-1,4-dihydronicotinami.de,

of base whereas

good yield

214,

to FeL33+ (L = bpy, phen) was investigated

The nicotinamide two-electron

R= CHO

and of L-dopa

or to poly(D-glutamate)

ibn proceeded

absence

213,

(L = 2,2*:6P2n:6W2"'-tetrapyridyl)

poly(L-glutamate)

model

C@H

(213), a product

(214) originates nitine

metal

H02C

216

(215)

(216) in

426 Ferric

chloride

oxidizes

(217) to (218) in 5% yield

1,2,3,4-tetrahydro-9H-carbazole

[5493.

218

217 The-oxidation

of trimethylamine

gave formyldimethylamine and the oxidant species species. salts

first order

The reaction

in aqueous medium

and was first order both in the substrate

[5501. Ferricyanide

formed by disproportionation

is kinetically

by Fe(CN)iion oxidation

of acridine

of lo-methylacridinium

rate is pa-dependent

15511. The pyridinium

(219) (R = Me, Ph; R' = Me, Et, Ph) were oxidized

in aqueous

KOH and EtOH to give pyrroles

Me, Et, COPh)

cation

in each Fe(C!N)z- and total acridine by K3Fe(CN16

(220) (R = Me, Ph; R' =

[5521.

Ph

A4,

219 Ph

Ph

A The kinetics amides

Py+

of the oxidation

of N-substituted

into the corresponding

(222) was studied.

PYH; and PyH' species

H

220

R'

R

PyH2 (221) by Fe(CN)i-

derivatives

If

The proposed

as intermediates

H CONH;!

[553].

dihydronicotinpyridinium

mechanism

involves

427

The oxidation cyanide,

of mesidine

dichromate

(223) in methanolic

and persulfate

taining

a shifted

product

(225) formed

methoxymethyl

afforded

group

by oxidative

media

an anil

in addition

dealkylation

by ferri-

(224) con-

to the principal

15541.

Me

0 Me

Mrt

Me

The kinetics cenium

cation

reported.

and several

transfer

Aromatic

e)

of the oxidation

substituted

were consistent

of NADH by ferrocations

ferrocenium

was

with a rate-limiting

one-

15551.

primary

give azobenzene See also

and mechanism

The results

electron

225

224

223

amines

desivatives

were oxidized in U-25%

using AgNO3

yield

or AgOAc

to

[5561.

E5201.

Oxidation

of

P-, S- or Halogen-Containing

Organic

Compounds Phosphorous

ylides

R3P=CH2

are oxidized

by CuCl2

in anhydrous

THF at low temperature to ethylidene-1,2-bis-phosphonium + i R3P -CH2CH2-P R3 15571. Aromatic

thiols

chlorochromate the Cx(VI)

were

involves

two-electron The oxidation

to disulfides

E5581. The &zoichiometry,

oxidation

of L-cysteine

and Cr(L-cysteinato); nism

oxidized

were

the formation reduction

kinetics

the sole products.

of CrlVI)

by pyridinium

and formation

[560]. Enantiomerically

nones

(230) were

prepared

these

first with

(Sf-N,S-d&methyl-S-phenylsulfoximine

References p. 435

(228)

by a 15591.

ion CS2Ni

by

pure dihydroxycycloalka-

from cycloalkenones

and hydroxylating

mecha-

followed

of L-cystine

of the 1,2,3,4-thiatriaaol-5-thiolate

of

L-Cystine

The preferred

thio ester

MnOq was studied

the adducts

and mechanksm

have been studied.

of a chromate

salts

(226) by transforming

the individual

(227) into diastereoxners

428 of(228) with 0~0~. The resulting composed

into

triols

(229) were thermally

de-

(227) and (230) [5611.

(227) 0

228

-

226

OHOH

OH OH A

/ / I \

0

I

--o

NMe 229

A kinetic ester,and

study of the oxidation of cysteine, cysteine methyl by Cu(II)-2,9-dimethyl-l,lO-phenantroline

penicillamine

(dmp) complexes parallel within

was reported.

pathways

in which oxidation

1:l thiol complexes

1-Chlorindan 1-indanone See also

7.

was oxidized

sulfur occurs

and Cu(dmp)'+

by Na2Cr207

[5621.

in aqueous

H2S04 togive

[502, 5081.

Chemistry

The crystal tion catalysts

structures

[containing

tartrate,

Related

02, was determined metallacyclopentane

asymmetric

(R,R)-N,N'-dibenzyltartramide were determined

a selective

complexes

sulfide oxidation

reactions

The intermediate

complex

involved

of CuC12 into

and (R,R)-

catalyst

were prepared

alkene and hetero-

and characterized

catalyst suppressed

is transformed [567].

[566].

of norbornene

(232) and its thermal decomposition

is completely

using

in metal nitro catalyzed

(231) formed during oxidation

with 02 using PdClZN02(MeCN)2

epoxida-

15641. The stxuc-

15651. Several Pd(I1) nitrile,

alkene oxidation

epoxynorbornane

to Oxidation

of two Ti tartrate

respectively]

ture of RuBr2(Me2S0j4,

presence

of coordinated

of Cu(dmp)g+

with two

[563].

Coordination

diethyl

The results are consistent

in the into

429

OH

l&r Cl

__~

232

231

8.

Electrooxidation The Ru(IV)

pyridinef dation

complex

of alcohols,

or aromatic Ru complex principal chemical

aldehydes,and

groups.

electrochemical chemical

~R~(~rpy)(bp~)(~)l'+

can be used as a catalyst The RufIV)

oxidation

LRuCl3

C-H bonds adjacent

complex

products oxidation

of alcohols

by the

are aldehydes was carried

[5681. The

the autoxidation

in basic

alcoholic

and ketones.

and electro-

solution.

The catalyzed

out in presence

oxi-

to olefinic

is regenerated

of [Ru(II)(trpy)(bpy)(H20)]2f

(L = 233) catalyzes

oxidation

(trpy = 2,2',2"-ter-

for the electrocatalytic

of lutidine

The electro [569].

Me 233

N-Proceted

aliphatic

red in excellent

yields

RuO2. 2H20 or RuC13 oxidizing

agent

in a saturated

is Ru04

cl N

hoEt 234

Referencesp.435

amines

like

(234) could be electrooxidi-

into the corresponding gaCl-acetone

amides

using

system.

The active

[5701.

0

cl

92% N I cooEt

430 Electrooxidation with Ag(bpy)+ reactions

of 4-methylpyridine

in propylene

carbonate

and 2,6_dimethylpyridine

as solvent was studied. The

involve mixed Ag(I1) bpy-methylpyridine

complexes

[5711.

V. -Reviews Homogeneous [5721.

catalysis

Homogeneous catalysis of organic reactions 237 refs. [573]. ions. Catalysis ditions.

by complexes

Of metal

of transition metal complexes under phase transfer con58 refs. 15741.

Noble metal catalysts 28 refs. 15751.

in the manufacture

Platinum metal complexes Catalysis

250 refs.

by transition metal complexes.

as catalysts.

of organic compounds. [5761.

by complexes with palladium-palladium

The catalytic

activity

bonds.

of some Rh(I) compounds.

15771.

38 refs.

15781.

Basic principles of the catalysis of conversions of unsaturated hydrocarbons by clusters of metal carbonyls. 33 refs. [5791. Homogeneous catalysis with metal phosphine introduction. 46 refs. 15801.

complexes.

A historical

Structurally characterized transition-metal phosphine relevance to catalytic reactions. 94 refs. [5811.

complexes

of

Functionalized tertiary phosphines and related ligands in organometallic coordination chemistry and catalysis. 54 refs. [582]. Polydentate 15831. Binuclear, 153 refs.

ligands and their effects on catalysis. phosphine-bridged [5841.

Polymer-bound

phosphine

Gel-immobilized Technological

complexes:

catalysts.

metal-complex perspectives

progress

150 refs.

catalysis.

67 refs.

and prospects.

[5851.

15861.

for anchored catalysts.

Hydrogen and carbon monoxide as ligand combination elements. 75 refs. [5881. The impact of transition metal-based homogeneous industrial processes. 14 refs. [5891.

12 refs.

[5871.

for transition

catalysis

in

431

Platinum carbonyls and their use in homogeneous 288 refs. L5901.

catalysis.

Homogeneous catalytic hydrogenation of carbon monoxide: ethylene 219 refs. glycol and ethanol from synthesis gas. [5911. Factors which determine product selectivity genation of carbon monoxide to oxygenates. Supported 58 refs.

clusters 15931.

and mechanism

Do we know the mechanism

of carbon monoxide

of hydroformylation?

Hydrogenation and hydroformylation radicals or otherwise. 14 refs. Hydroformylation.

127 refs.

Some aspects of hydrogen

in homogeneous hydro190 refs. L5921. reduction.

30 refs.

with HCo(C0)4 L5951.

[5941.

and HMn(C0)5:

[596].

activation

in hydroformylation.

32 refs.

[5971.

Hydroformylation Regeneration

of unsaturated

of hydroformylation

fatty acids. catalysts.

74 refs. 112 refs.

[5981. t5991.

Hydrogenation and hydroformylation reactions using binuclear diphosphine-bridged complexes of Rh. [6001. 97 refs. Homogeneous

catalysis:

Recent advances [602].

a wedding

in homologation:

of theory and experiments. the effect of promoters.

[6Ol]. 26 refs.

Coordination chemistry of the carbon dioxide molecule: biological, chemical, electrochemical and photochemical activation. 203 refs. [6031. New stoichiometric and catalytic organometallic chemistry with actinides. C-H Activation and phosphine/phosphite chemistry. 68 refs. [604]. The effect of net ionic charge on the catalytic hydrides. 15 refs. [605]. Cationic

rhodium

and iridium complexes

behavior

in catalysis.

of metal

66 refs.

cis-Alkyl and cis-acylrhodium and -iridium hydrides: model aiates in homTeneous catalysis. 38 refs. [6071. Transition metal hydrides 27 refs. L6081.

in homogeneous

catalytic

Kinetics and mechanism of reversible insertion acetylenes into early transition metal-hydride [609]. Hydrogenation of vegetable 131 refs. [6101.

References p.435

oils by transition

inter-

hydrogenation.

of olefins and bonds. 29 refs. metal

[6061.

complexes.

432 Organometallic

catalysis

in asymmetric

synthesis.

DIOP as a ligand in asymmetric catalysis phosphine complexes. 60 refs. 16121.

67 refs.

[6111.

using transition metal

Asymmetric hydrogenation in the presence of bis diphenylphosphinic 25 refs. [6131. complexes of Hh. Asymmetric hydrogenation reactions complexes of rhodium. 102 refs. Problems of asymmetric 47 refs. 16151.

using chiral diphosphine 16141.

hydrogenation

Asymmetric hydrogenation on metallic ric catalysts. 149 refs. L6161.

with complex catalysts. and metallocomplex

dissymmet-

Homogeneous asymmetric catalysis by means of chiral Hh complexes (hydrogenation and hydrosilylation). [6171. Hydrogenation reactions of carbonyl and C=N functions 97 refs. complexes. 16181. Catalytic

hydrogen-transfer

reactions.

Thermodynamics of oxygen binding complexes. 599 refs. [6201. Phthalocyanines in catalysis.

331 refs.

using Rh

[6191.

in natural and synthetic

100 refs.

dioxygen

16211.

Catalytic properties of water-soluble phthalocyanine complexes 64 refs. in redox reactions of sulfur compounds. [6221. Metalloporphyrins as chain transfer catalysts in radical polymerization and stereoselective oxidation. 44 refs. [6231. The role of transition reactions. 36 refs.

metal salts in one electron 16241.

Homogeneous-phase oxidations catalysed advances. 200 refs. 16251. Transition-metal peroxides and homolytic liquid-phase Catalyzed ligand-phase 118 refs. [6271.

transfer organic

by transition

metals:

recent

as reactive intermediates in heterolytic catalytic oxidations. 23 refs. 16261.

oxidation

of olefinic hydrocarbons.

Metal nitro complexes as oxygen transfer agents: selective oxidation of organic substrates by molecular oxygen. 48 refs. 16281. Homogeneous complexes. Oxidations

catalysis of oxidation 148 refs. [6291. with vanadium(V).

reactions

131 refs.

using phosphine

[6301.

Synthetic applications of palladium-catalyzed to ketones. 120 refs. 16311.

oxidation

of olefins

433 List of Abbreviations acac

=

acetylacetonate

Boc

=

t-butoxycarbonyl,

BPPM

=

see Fig.

bpy COD

=

2,2'-bipyridine

=

1,5-cyclooctadiene

CP

=

q5-cyclopentadienyl

CY (-)-DIOCOL

=

cyclohexyl

=

see Fig.

(8)

(-)-DIOP

see Fig.

(7)

dmgH DMSO

dimethylglyoxime

tBuOC(O)-

(55)

dimethylsulfoxide

dmPm

bis(dimethylphosphino)methane,

Me2PCH2PMe2

dpm

bis(diphenylphosphino)methane,

Ph2PCH2PPh2

dppe HD

bis(diphenylphosphino)ethane,

Ph2PCH2CH2PPh2

MS

methylsulfonyl

NBD

norbornadiene

1,5-hexadiene (mesyl), CH3S02-

nmen

neomenthyl

OEP

octaethylporphirinato

0.y.

optical

phen

l,lO-phenanthroline

salen

N,N'-bis(salicylidene)-ethylenediamino

SIL

silica

st

stearate,

yield

nC

17H35C00 trifluoromethylsulfonyl

Tf tpm TPP

triphenylphosphine

Ts

p-toluenesulfonyl

Metal Ti

(triflyl),

m-monosulfonate,

CF3S02PPh2(C6H4S0i)

5,10,15,20-tetraphenylporphirinato (tosyl) p-CH3C6H4S02-

Index 90, 136, 179, 180, 227, 249, 250, 256, 208, 402-411,

459, 471,

564 Zr

289, 437

Hf

317

v

7, 90, 339, 340, 345, 358, 384, 412, 413, 420, 459, 476, 503-505

Cr

30, 75, 84, 90, 91, 130, 228, 245, 246, 251, 252, 285, 287,292, 358, 388-390,

Referencesp.435

395, 405, 438, 477-482,

506-517,

558, 559, 563

434

MO

39,

75,

303,

84,

306,

499-501,

90,

308,

161, 332,

75,

84,

91,

245,

Mn

62,

74,

84

, 135,

312,

313,

481,

483-488,

Tc

431

Re

93,

134,

Fe

36,

39,

322,

74,

247,

75,

82-85,

258,

358,

349,

350,

442-445,

517,

263,

83,

206,

8, U-20,

165,

130,

396,

157-159,

258-262,

305,

307,

310,

358,

360,

361,

366-368,

430,

455,

458,

496,

5, 10,

166-168,

178,

272,

313,

376,

377,

533,

20-35,

43-46,

69-73,

164,

169-171,

178,

204,

206,

209-211,

263,

264,

268,

298-300,

600,

606,

607 206,

212,

127-129,

534,

51,

606, 159,

329,

73,

77,

195,

221,

469,

134, 233,

380,

84,

196,

287,

433,

88,

205,

288,

89,

208,

295-297,

333,

343-345,

349-355,

379,

381-383,

398,

80, 182,

213,

84,

86,

183,

418,

92,

187,

95,

112-129,

191-193,

222-224,

230,

236-238,

334-336,

378,

399,

213,

221,

226,

231,

578,

232,

607 165,

344, 96,

178,

355,

183,

468,

131-133,

220,

470,

264,

500,

172-178,

183,

276,

277,

280,

301-304,

400,

434,

454,

456,

490,

566,

567,

577

183,

184,

202,

214,

267,

266,

272,

279,

535

265,

590

392-395,

561

73,

264,

577,

341,

466,

376,

495, 71,

243,

134,

203,

335,

103-106,

219,

375,

225,

87,

185,

595

244,

130,

461,

568-570

202-284,

315-327,

497,

387, 464,

94,

218,

466,

63-68,

199,

328,

310,

595

314,

386,

84,

565,

454,

240,

73,

309,

421-430,

160-162,

463,

273-275,

532,

397,

83, 207,

52-58,

264,

311,

271,

195,

76,

305,

312,

374, 461,

79,

206,

138-156,

3, 54,

475,

540

560,

130, 305,

366, 460,

134,

47,

459,

546-555

531,

48-50,

234,

239-242,

Pt

240,

220,

288,

290-292,

418,

541-545,

117,

78,

270,

494,

38-42,

107-111,

93,

186-190,

264,

co

39,

269,

439-441,

474,

294,

391,

304,

359,

536,

71,

181,

OS

9, 37,

266,

459,

293,

385,

288,

450,

525-530,

55-62,

171,

240,

288,

379,

98-102,

286,

432,

38,

303,

517-524,

267,

345,

1, 4,

257,

414-420,

217

462-465,

Pd

512,

430,

10-12,

253, 412,

292,

272,

358,

342,

238,

Ni

254,

345,

445-453,

Ir

278,

427,

162-164,

Rh

246,

502,

194,

489-493, RU

389,

540

W

206,

229,

206, 385,

197-202, 330,

268,

214,

344,

309,

362,

435,

457,

435 cu

97, 130, 248, 255, 281, 288, 301, 302, 312, 322, 331, 337, 338, 344, 346, 347, 356-358,

363-366,

369-373,

401, 430, 436, 454, 458, 467, 468, 536-539, Ag

312, 362, 536, 556, 571

Au

472

Th

137

Transition

6, 81,

general

metals,

379, 389,

557, 562

348

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Perkin

Trans.

Y.Kurasawa

and

T.Kinoshita,

Heterocycles

1231. L-Ernst,

G.Dasqupta 393;

23

673.

Z.Naturforsch. 550

Biopolymers

125828.

Y.KQndo

Y.Okamoto, 22

549

(1984)

S.Fukuzumi, II

548

101

and M.Farinella,

101

39B

B.P.Das, (1984)

and M.X.Mahanti, (1984)

6396.

B.Choudhury

and

D.N.Chowdury,

817. React.Kinet.Catal.Lett

23

(1983)

465

551

J.W_Bunting

552

P.Nesvadba 543;

553

CA

and

G.M.Kauffman,

and

101

M.F.Powell,

J.Kuthan,

Can.J.Chem.

62

(1984)

729.

Collect.Czech.Chem.Commun.

(1984)

54871.

J.C.Wu

and

T.C.Bruice,

49

J.Am.Chem.Soc.

106

(1984)

(1984)

3850. 554

S-L-Goldstein

555

B.W.Carlson,,L.L.Miller, Sot.

556

106

557

and

E.McNelis,

559

D.W.J.Kwong

560

W_L.Polito

and

14 and and

4th

(1984)

717;

E.F.A_Neves,

(1984)

CA

100

G-D-Stevens

and

R.A.Holwerda,

563

R.Nowicki (1984)

Z.Naturforsch.

and

K.Mazan,

(1984)

and

J.Toofan,

170205.

Inorg.Chem.

(1984)

562

23

(1984)

2528.

90133.

J.Am.Chem.Soc. Inorg.Chem.

Pol.J.Chem.

57

106

23

(1984)

(1984)

(1983)

645;

2459.

2777.

CA

101

72395.

I.D.Williams,

106

565

J-D-Oliver

D-P-Riley,

566

M.A.Andrews,

and

(1984)

F.Chauvet,

Inorg.Chem.

and

23

C.-W.F.Cheng,

J.Am.Chem.Soc.

A.Heumann

and

S.J.Lippard,

6430.

T.C.-T.Chang,

T.F.Koetzle,

(1984)

K.B.Sharpless

S.F.Pedersen,

J.Am.Chem.Soc.

106

B.Waegell,

(1984)

156.

T.J.Rnge,

(1984)

K.P.Kelly

5913.

Tetrahedron

Lett.

25

4393.

M.S.Thompson, 49

569

R.R.Gagne

570

S.Torii,

W.F.De

(1984) and

Acta

D.N.Marks,

Y.Le 29

Giovani,

B-A-Moyer

and

T-J-Meyer,

J.Org.

4972.

T.Inokuchi

J.Talarmin, chim.

159;

An.Simp.Bras.Electroquim.Electro-

7; CA 101

M.R.Barbachyn,

571

J.Am.Chem.

A.Sardarian

CA 101

D.E.Pennington,

and

them.

(1983)

H.Schmidbaur,

H.Parham,

C.R.Johnson

568

1613.

618.

561

567

J.Grodkowski,

J.Chem.Soc.Pak.5

H.Firouzabadi,N.Iranpoor,

and

(1984)

7233.

C.Dbrzbach

Synth.Commun.

564

and

49

120596.

(1984)

anal.

J.Org.Chem.

P.Neta

Y.Hayat,

G.A.Bowmaker, 39B

558

(1984)

M.Z.Iqbal (1984)

and

and

Mest,

(1984)

Inorg.Chem. T.Yukawa, M.L'Her

1037;

CA

and 101

23

(1984)

Chem.Lett.

65. (1984)

J.Courtot-Coupez, (1984)

218363.

1063. Electro-

466 572 573

C.White, CA

574

100

576

100

Fundam

and

(1984)

Itogi

13,

J.Chatt,

585

586

239;

D.W.Meek,

CA

CA

111;

100

(1984)

79;

CA 100

21

(1983)

404;

(1983)

565;

CA 100

VINITI.

Kinet.Kataliz

190616. 14

(1984)

53; CA

101

Itogi 213;

D.Valentine (1982)

and 608;

F.Calderazzo,

589

W.Keim,

893. Complexes

(1983)

Homogeneous

CA

100

Catal.Met.Phosphine

(1984)

40318.

Catal.Met.Phosphine

Complexes

51649.

Catal.Met.Phosphine

Complexes

Catal.Met.Phosphine

(1983)

Complexes

(1983)

CA

Catal.Met.Phosphine

i Nauki 101

100

i Tekhn.

(1984)

A.Madovik, CA

Complexes

(1983)

40321. VINITI.

Kinet.

Kataliz

190617.

Prepr.-Am.Chem,Soc.,Div.Pet.Chem.

(1984)

Ann.N.Y.Acad.Sci.

Fundam.Res.Homogeneous

91954. 415

(1983)

Catal.

37.

4 (1984)

131;

198288.

H.C.Clark

1;

51648.

(1984)

I.I.Moiseev, 13,

(1984)

85744.

Homogeneous 100

10

(1984)

Homogeneous

588

590

i Tekhn.

Homogeneous CA

(1984)

N.L.Holy,

(1984)

68

Catal.Met.Phosphine

Homogeneous

CA'100

A.L.Balch,

27

J.Technol.

Oxford

(1984)

J.A.Ibers,

T.B.Rauchfuss,

(1984) 587

4 (1984)

40316.

(1983)

443;

i Nauki 101

Homogeneous (1984) and

167;

Indian

Koord.Khim.

Complexes

(1983)

584

Catal.

Contrib.Cient.Tcnol.

N-L-Jones

257;

416;

71791.

580

100

CA

Badal,

G.K.Magomedov,

583

G.R.Patel,

Sci.Prog.

147;

579

582

351,

40322.

R.Sariego

CA

2 (1984)

158516.

I.I.Moiseev,

(1984)

581

Res.Homogeneous

D.J.Cole-Hamilton,

(1984) 578

351.

138224.

(1984) 577

(1983)

) 208623.

P.N.Rylander CA

11

Mech.Inorg.Organomet.React. (198

H.Alper, (1984)

575

Organomet.Chem.

C.White,

and

V.K.Jain,

Coord.Chem.Rev.

55

(1984)

151.

CA

100

467 591

B.D.Dombek,

Adv.Catal.

592

L-Costa,

593

J.M_Easset,B.Besson,

32 (1983) 325.

Catal.Rev.-Sci.Eng.

25 (1983) 325.

A.Choplin,

M.Leconte,

Fundam.Res.Homogeneous

and A.Theolier,

D.Rojas,

Catal.

A-K-Smith

4 (1984) 19;

CA 100 (1984) 138222. 594

L.Markb,

Fundam.Res.Homogeneous

Catal.

4 (1984) 1; CA 100

(1984)'138221. Ann.N.Y.Acad.Sci.

595

M.Orchin,

596

B.A.Murrer

415 (1983) 129.

and M.J.Russell,

Catalysis

(London)

6 (1983) 169;

CA 100 (1984) 209089. 597

P.Pino,

598

E.H.Pryde,

Ann.N.Y.Acad.Soi.. 415 (1983) 111. J.Am.Oil

Chem.Soc.

61 (1984) 419; CA 100 (1984)

123136. 599

J.Alexandr,

M.Elbert

and M.Polievka,

Ropa Uhlie

26 (1984)

457; CA 101 (1984) 194072. 600

A.R.Sanger,

Homogeneous

Catal.Met.Phosphine

Complexes

(1983)

215; CA 100 (1984) 68337. 601

M.Orchin,

Catal Rev. - Sci.Eng_

26 (1984) 59; CA 100 (1984)

84898. 602

W.R_Pretzer Chem.

and M-M-Habib,

(Proc.Symp.)

Plenum:

R.Zeissel,

Nouv.J.Chim.

604

J.W.Bruno,

M.R.Duttera,

Inorg.Chim.Acta R.H.Crabtree, 415 606

Gas Alcohols

New York, N-Y.; CA 101 (1984) 89905.

603

605

Catal.Convers.Synth.

(1983, Pub. 1984) 261, Ed. by R-G-Herman,

7 (1983) 613; CA 100 C.M.Fendrick,

(1984) 153767.

G-M-Smith

and T-J-Marks,

94 (1984) 271. D-R-Anton

and M-W-Davis,

Ann.N.Y.Acad.Sci_

(1983) 268.

R.H.Crabtree,

Homogeneous

Catal.Met.Phosphine

Complexes

(1983) 297; CA 100 (1984) 40319. 607

D.Milstein,

608

J.Halpern,

609

N.D.McGrady,

Acc.Chem.Res.

17 (1984) 221.

Ann.N.Y.Acad.Sci. C.McDade

415 (1983) 244.

and J.E.Bercaw,

Organomet.Comp.Synth.

Struct Theory,

Proc.Symp.Ind. -Univ.Coop.Chem.Program.Dep.

Chem.,Tex.A&M

Univ.

(1983) 46; CA 100

(1984) 6581.

468 610

V.Vaisarova,

P.Svoboda,

J.Soucek

and J.Hetflejs,

Chem.Listy

78 (1984) 737; CA 101 (1984) 132897. 611

P.Pino and G.Consiglio,

612

J.Weishaeupl,

Pure Appl.Chem.

8sterr.Chem.Z.

55 (1983) 1781.

85 (1984) 1; CA 100 (1984)

155856. 613

V_A.Pavlov Khim.

614

615

and E.I.Klabunovskii,

Homogeneous

SSSR, Ser.

Catal.Met.Phosphine

J-M-Brown

and P.A.Chaloner,

Complexes

(1983) 137; CA 100 (1984) 190943. Wiss.Z.Ernst-Moritz-Arndt-Univ.Greifsw.,

H.Pracejus,

Reihe

Naturwiss. 616

E.I.Klabunovskii,

617

I.Ojima,

618

B.Heil,

L.Markd

Math.-

31 (1982) 5; CA 100 (1984)208657. Izv.Akad.Nauk

Pure Appl.Chem.

Complexes 619

Izv.Akad.Nauk

(1983) 2015.

SSSR, Ser.Khim.

(1984) 505.

56 (1984) 99; CA 101 (1984) 38793.

and S-T&%%,

Homogeneous

Catal.Met.Phosphine

(1983) 317; CA 100 (1984) 120124.

V.M.Gryaznov,

Fiz.Khim.

(Moscow) (1982) 96; CA.100

(1984)

208650. 620

E_C.Niederhoffer,

J.H.Timmons

and A.E.Martell,

Chem.Revs.

84 (1984) 137. 621

M_Hronec

and J.Ilavsky,

Petrochemia

22 (1983) 89; CA 100

(1984) 13141. 622

V.E.Maizlish Tekhnol.

623

Izv.Vyssh.Zaved.,Khim.Khim.

27 (1984) 1003; CA 101 (1984) 236107.

L.V.Karmilova, Usp.Khim.

624

and V.F.Borodkin,

F.Minisci,

G.V.Ponomarev,

B.R.Smirnov

and I.M.Bel'govski,

53 (1984) 223; CA 100 (1984) 121633. Fundam.Res.Homogeneous

Catal.

4 (1984) 173; CA 100

(1984) 138225. 625

B.Meunier,

Bull.Soc.Chim.Fr.

(1983) 11-12, Pt. 2, 345; CA 101

(1984) 89882. 626

H.Minoun,

Spec.Publ. -R.Soc.Chem.

(1984) 48, 120; CA 101

(1984)

210070. 627

D.Schnurpfeil, Merseburg

628

Wiss.Z.Tech.Hochsch.

26 (1984) 411; CA 101

"Carl Schorlemmer"

Leuna-

(1984) 190614.

F-Mares and S.E.Diamond, Fundam.Res.Homogeneous (1984) 55; CA 100 (1984) 138223.

Catal.

4

629

630

D.M.Roundhill,

Homogeneous

(1984) 120104.

D.K.Babel,

R.Shanker

R.Banu,

43 (1984) 250; CA 101 631

Catal.Met.Phosphine

(1983) 377; CA 100

J.Tsuji,

Synthesis

and G.V.Bakore,

(1984) 117446.

(1984) 369.

Complexes

J.Sci.Ind.Res.