Metal cluster catalysis

c43

Journalof

Organomstallic Chemistry, 1’78 (1979) C43-C49 0 ElsevierSequoiaS.A.,Lausanne-Printed in TheNetherlands

Preliminary communication

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METAL CLUSTER CATALYSIS

III*. SELECTIVE HO~lOGENEOLJS HYDROGENATIONS CATALYZED BY 1(r1~-c~H~)Fe(u~-CO)l,

U. Pittman, Jr.,

Charles

Department

The

of Chemistry,

University

PIcCee,

of Alabama,

University,

35486 (U.S.A.)

Alabama

and

Robert C. Ryan, John

P. O'Connor

James

Department

University

of Chemistry,

of Wisconsin-Zladison,

.

Lladison,

53706, (U.S.A.)

Wisconsin

(Received June Filth, 1979)

Summary

The

iron

hydrogenation

cluster,

[(~'-C5HS)Fe(u3-CO)]4,

of alkynes

selective reduction

of

co alkenes

nitro

carbon-carbon

double

The

cluster

was

unchanged

95-97Z

yields

containing solution

groups bonds

concentration, after

were

filtered

and

100-1000

psig

and

the

Internal alkynes are slowly reduced to cis

to aniline (methyl

and

1410

by high

After

terminal are

pressure

liquid

Cluster

1 was

(1000 180

and

acrylonitzrile)

turnovers.

reduction

detected.

through

derivatives,

acrylate,

monitored

afrrer catalytic

species was

1148

lOO-130°

the selective

terminal alkynes to olefins in the presence of

alkenes or internal alkynes. olefins, aryl

at

1, catalyzes

turnovers) turnovers.

an ultrafiltration

membrane

vessel where hydrogenation of I-pentvne continued.

and the

activated hydrogenated.

chromatography, isolated no

in

other

iron-

catalyst

into

a second

Fragmentation of 1 tc

c44

($-CgHs)Fe(CO)pH gives

this

iron

reductions_ cluster

appears to be ruled out since [(q5-C$i$Fe(CO)212, hydride

Thus

catalyst

Ghen

cluster

wltich resists

to metal-metal

__

~_.--__--__.-.-___.~__.

The has

use

been

catalysis of small

only

a modest

to be

the

monoxide giycol

synthesis

the hydrogenation complexes little with

attention carbon

styrene

problem

conditions

bonds.

is

in

regard

in

in the

for

the bonding

[31,

of clusters

where

the

rhodium

clusters

reduction

cluster

of

anions

by homogeneous

clusters

have

seem carbon

olefins

the presence

[S]_

While

mononculear

received

Activated

presence

of

models

[4] and the formation of ethylene

by

171.

studies

behavior

include

as catalysts

as possible

reactions

alkynes

[61,

with

to fragment COAX

relatively were

reduced

of Rh6(CO)16

of Co4(CO)12,

use

WC haiie a+ocated

and

toset!ler both ligands

[I, ?a,

of alkynes.

[(75-CgHg)Fe(:~3-CO)]4 other

by

irons

and

b)

[8] and

Co3Xh(CO)l?_,

and

in catalqis

is

moieties

pioneered

activated _I_

In

One

the

use

we

and

report

olefins, cluster

of

1 each

triply-bridging

to avoid

stronger

first

nitro iron

carbonyl

frag-

metal-metal

row

by stable, here

and

reaction

[ll, 121

approach

w!lich have

bonds

Indeed,

under

[(G5-C5aj)Fe(C0)21~

row clusters

2~1.

three

of clusters

reactions.

metal-metal

[13],

use

homonuclear

(101 and

hydroformylntion

the

the

into

third

hydrogenation

three

and

of

bound

bridging

cxtal>Fzed

associated

['a-cl. during

mentation

ligands

row

[91.

propensity

fragment

Examples

and water

is hydrogenated

A key

are

this

monoxide

CO+h~(CO)l~

their

gas

intense

document

practiced

in

of a first

compounds

[l,?]

fluxional

of Ir&(CO) 12

of olefins

is widely

example

to bridging

cluster

interest

and

Cl].

in the presence from

third due

Despite

[21.

of reports

catalysts

metal

research

to clusters

number

true

fragmentation

transition

surfaces

molecules

the

active in I-penryne

not

-

intense

at metal

to be

was

bonding.

of soluble

an areaof

in hydrogen,

1 appears

addition

__

heated

which

clusters

that

nonflusional,

the selective groups atom

catalyzed is bonded

ligands.

by to a)

In each

c45 case,

1 was recovered in 95-972 yields from the reaction

solutions after

long reaction periods and molar turnovers in excess of 1000.

Isolation

and tic analysis revealed no other iron containing compounds.

1

c3n7cscn

> C3H7CH=CH2 Hp(lOO-1000 psi) 160-1300

The hydrogenation of l-pentyne to 1-pentene was readily catalyzed by 1 at lOO-140° using hydrogen pressures from 100 to 1000 psi.

The cluster

was first dried by heating at 80" and 0.1 torr (where 2 is stable and its IR spectra is unchanged)_ and isomerization

In general, the selectivity

to 2-pentene is very slow.

to I-pentene is high,

At high conversions,

this

selectivity decreased from -65% to -75% as the pressure increased from 100 to 250 psi nnd then remained unchanged to 1000 psi. lower conversions, selectivity was higher. a 98Z selectivity conversion.

to I-pentene

At 46% conversion

At

(120°, 100 psi),

obtained which decreased to 92% at 65%

At long reaction times, 1 does not promoce

in contrast to the homogeneous RhCl(PPh3)3

wzs

(See Table 1).

catalysts

olefin hydrogenation

[Rh(XBD)(PR3)7]+PF6-

[6c] and

[14] which effected rapid olefin hydrogenation once alkvne was

esausted. Internal alkynes are hydrogenated more slowly than terminal alkynes. A 1:l misture of 1-pentyne and 3-hesyne, after 11 h at 100 psi and loo", gave a 62% conversion of l-prntvne to l-pentene (93.5:;selectivity) and only a 4% conversion of 3-hesyne to cis-3-hesene reduction of terminal alkynes contrasts [Rh(NBD) (PR3)21+P1'6-

(ZOO.2selectivity).

The faster

shraply with the use of

catal>*zed the hydrogenation of internal [6cl wlich 1

alkynes more rapidly than terminal alkynes. !&ile catalvsis by a cluster cannot be definitively proved fragmentation of 1 appears unlikely in these reductions.

Xot

[?I, the

only

was

1

100 105 460 685 980 504 460 100 100 300 100 100 100 100 100 300

120 120 12u 120 120 120 130 100 100 130 100 100 100 100 100 130

1-Pcntyneb

1-PcnLync

II

II

0,

2-Pentync

I-Pentcnc

1,3-Cyclooctadicne

Nitrobeneene

II

Elethyl acrylatc

Acrylonitrl.le

Ethyl crotonate

Bcneonitrile

Ilethyl

bCa talyst

1,

1-pantenc 1-pentcne

83 98 62

46

24

24

24

24

24

24

24

26

24

57

40

70

120

at 80°C, 0.1 torr,

Propionitrilc

26

for 1211prior

benzene

0

0

0

substrate to reaction.

(15 ml),

Ethyl butarate

(31)

(20.3 mmol).

(2.3)

(26)

Methyl propnnoa te (32)

32 2.3

aniline

(6)

anilJ.ne

6 31

cyclooctene

(0,2) (6)

pentane (2,9),

(55),

pentane

pentane

(0.8)

(21,4)

(17)

(3,O)

(3.8)

(13,7)

pentane

pentane

(O), pentane

(2,6),

(4,2),

(lO,l),

(8,8),

(% yield)

pentanc

2-pentcne

(48), (4,2),

2-pentenc

cyclooctnnc

2-pcnlcne

2-pentcnc

(73))

2-pcntene

2-pentcnc

(61),

(84))

(73),

Products

3.7

61

2-fientene

I-pcntcne

99

4.4

1-pcntene

85

G 88

1-pentene

Conversion %

Catalyzed

Time I1

Homogeneous Hydrogenntions by ~(ll5-C5n~)~c(~3-Co)l~.~

employed 0.05 mmol of catalyst,

1 was dried

“Each reaction

Nitropropane

ethyl

Ketone

Pressure Psi

Substrate

Temp, oC

Table

isolated

in high

periods

in boiling

oxidations more,

difficult

high

did

not

after

vessel

results that

nitriles

occurred

and

were

through

hydrogenation

clusters cluster

psi

as

The

(125O.

of

60C

active

bridging

H2)

130,

solutions

using

iron

was

clear;

observed. the

into

an induction

will

1148,

benzene),

membrane

catalyst,

was

418,

remained

l-pentyne,

ligands

of

concentration

after

without

Furtherit is

psi

catalyst

ultrafiltration

the

.

concentration

colloidal

H2,

long

multiple

hydrogen,

(9.7X)

continued

with

resisted were

hydrogenation

period.

supporting

the

be a fertile

inert.

conditions

Sitrobenzene

but

at

terminal but at

the water-gas

olefins internal

and

1.

area

was

only

300

such

psi

Similarly, 6% converted

a 31%

as methyl

activated

Further

reaction, studies

conversion

acrvlate

olefins

1 did not catalyze

100°. shift

of olefins.

130°

using

and

(ethyl

the hydrogenation

hydroformylation. are

underway

or

in our

laboratory_ One

might

conditions.

suggest

Thus,

[n5-C5H5Fe(CO>2]2, with did from

hydrogen. not

catalyze

these

which At

1 fragments

attempts

were

reduction

must

made

is known

temperatures

reactions.

to n5-C5H5Fe(C0)2H

that

of

Thus, not

to n5-CgHgFe(C0)2H to hydrogenate

to generate

from

lOO-120°

l-pentyne. in reactions

occur.

under

1-pentyne

n5-CgHgFe(C0)2H (loo-400

psi)

reaction

using when

heated

the dimer

Furthermore,

1 was

catalyzed

1, fragmentation

by

not

reac-

a second

catalysis.

reduction

alkoxycarbonylation

600 an

1.

The

for

fragmenting.

and

reaction

no evidence

hydrogenated

monoxide,

the

(125",

Activated

resisted

carbon

detection

these

in 24 h.

crotonate)

limits

groups

under

'acrylonitrile

(UPLC)_

undergo

without

species

chromatography of HPLC

it is stable

of alkyne

hydrogenations

olefins,

and keto

-1)

reform

1 functions

row

like

(Oa

l-pentyne

filtered

to explore

to aniline

it could

turnovers

suggest

Dienes,

[151'to

the presence

light

where

first

for others

of

280 was

J is known

Additionally,

scatter

sclutron

These

the

turnovers_

reaction

idea

liquid

within

Finally, tion

how

but

reduction

in

during

pressure

1410

they

fragment

monitored

Also,

and

reduction,

each

xylene.

to imagine

unchanged and

after

(0+-i-l-2)

if _1 did

_1 was

yield

recovered

c48

A

typical

Benzene were

(15 ml),

charged

was

flushed

hydrogen at

; (-030

into

the

three

After

The

2-pentyne

l-pentyne

0.05

placed

(1.6X),

and

conducted-as

under The

l-pentyne

reactor

solution

20'

(3.8%).

1-pentyne

W

was

(acid

and

the

was

then

constant

analyzed washed,

follows.

(2.0 ml,

nitrogen

in a preequilibrated

on chromosorb

pentane

was and

hydrogen-

programmed

were

mmol),

vessel

6 h the reaction

temperature

products

g.,

with

and

tricresylphosphate

mesh).

of

reaction

times

to 100 psi

tooo.

15%

hydrogenation

by DMCS

20.3

mmol)

reactor

(glass)

pressurized

with

temperature

bath

glc

[15' x l/8",

treated,

80-100

(6 min-).

lS'/min.

to 100°

(hold

1-pentene

(73-O%),

trans-2-pentene

10 min.)](8.8%),

(14.7%).

Acknowledgements This

work

CHE77-06810_

was We

for an initial

supported

thank

sample

by

Professor of cluster

the National L. F, Dahl, 1 and

Science

Foundation,

University

for his

continued

grant

number

of Wisconsin-Madison. interest

in

this

work_

Reference 1.

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(1977)

Pittman,

Ryan, CC.Pittman, Jr. and J. P. O'Connor, J. Am. 1986, b) R. C. Ryan, C. >I. Wilemon, If_ DalSanto, Jr., J. >lolec. Catal., 5(j) (1979) 319.

Chem. SOC. and C. D.

2.

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N. Sukamoto, and

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J. Tsuji

12_

E. Cesarotti, A_ 4, (1978) 205.

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R. B. King,

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J.

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P. Candlin

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60.