Cationic, neutral and anionic complexes of ruthenium(II) containing η6-arene ligands

121

Joumcl of Organometdic Chemistry, 162 (1978) 121-136 0 ElsevierSequoiaS.A.,Lausanne-Printed inTheNetberlands

Cationic, n6-Arene

D.R.

Neutral

and

Anionic

Complexes

of Ruthenium
containing

Ligands

Robertson,

of Chemistry, (Received

T.A.

University

August

and

Stephenson*

34th,

(in part)

T. Arthur,

Edinburgh

of Edinburgh,

ER9

Department

355 (Great

Britain)

1978)

Summary Reaction

of [(Ru(C6Hg)C19)3]

ethanol

gives

the

Cs[Ru~C6H5)C131 1OSeS

a

Me3S0,


chloride

VariOUS

Lewis PR3

methanol

bases

of


high

bridge with

PR3

compounds

complex

of

the

solution

although

reactions

various

Lewis

arene

cations

bases

this and

readily

reactions

[Ru
triple

chloride stable

produces

NHqPF5

the

in

bridged

in MeN03. and

complex readily Reaction

Me3SO.

new

monomeric,


[Ru
with

(L = C5Ii5N.

with

in water

in

of ruthenium

of [(Ru
which,

cleavage

arene

of CsCl/HCl

[Ru(C6H8)C12
the

yields

PF6
ruthenium
give

an excess

in aqueous

to gve

Reaction

etc).

[ Ru3
anionic

although

ion

gives

undergoes

first

with

Et3S,

&).

Introduction In recent [CR~1(arene)X3}~ 1.3.5-C6H3Me3. several a variety

workers

11-31.

(arene

[l-7

1

bases

(L = PR3,

reactions

= C6H6,

p-MeC6HqCHKez;

of Lewis

[Ru
some

years,

of the

C6H50Ne,

p- and

X = Cl or Br)

In particular,

bridge

to give

the

P
AsR3,

unusual

neutral, C5H5N

n6-arene

m-C6HeMe2,

have

been

cleavage monomeric etc)

are

complexes C6H5Ne,

investigated reactions

by with

complexes well

documented

122 In this of

the

paper,

benzene

we now

anion

reactions

Results

and

(CyR8))Sl

(CyH8

(PhCH2)P+.

Cs+)

complex

earlier

mixture gave

always

stretching

contain

either

be

to make by

the

(C8H8)C12)2]and a 10

unavoidable that

1

H nmr

dissociation

details

of

al and

at 280

and

cm

to one

thus,

of the

corresponding

h¶Cl/RCl

of

the

presence -1

the

of

several (II) free

v
days

although of CsCl.

to terminal

band

bands.

CQv

at 280

cm

band

symmetry -1

at

Unfortunately,


or Cs[Ru
a

coordinated

or a weak

[Ru(C8H6)X3]-

being

with

(II) posesses

modes

been

using

(1)

for

anionic

now

complex

assigned

broad

(M = Ph3-

first

has

completely

compound

e vibrational

[{Ru(C,H~)X~}~]

I-)

with

from

the

anions, X- were

reaction

case. Cs[ Ru(C,$)ClS]

dm

-3

presence studies of

yield

in ethanol

the

Since

expected

an aqueous

mol

with

ruthenium

complex

indicated band

[{Ru(CO)ClS-

for Cs[Ru
this

of [{Ru(C~H~)X~)~]

only

in each

-3

with

[ Ch(C6H6)Ci212]

HCl

closely

(II)

assigned

As expected,

for

the

reaction

unsuccessful, mixture

bridged

An attempt

n6-arene

concentrated

a broad

were

both

could

attempts

formation

bases.

compound

a high

shaking

vibration(s).

bands

gave

Thus.

to obtain of

contained

v(RuC1)

cm

Lewis

of the

anionic

analysing

spectrum

u(RuC1)

298

the

together

~Ru
and

difficult

i.r.

-1

of

chloride

hepta-2,5-diene)

acetone

route.

powder

and

might

triple

various

reaction

first

CsCl

benzene

txo

the

preparative

mull

with

t2.2.11

of ruthenium

an orange

The

CSJ,

in degassed

of excess

it was

the

181

of Cs[Ru(C_R,_)C13] "V

= bicycle

to synthesise

a similar

and

results

[~Ru(C~H~)C~~)~,

compounds

reactions

As reported

made

full

Discussion

a) Synthesis

diene

from

of these

and

the

[Ru
cation[C8H8RuC13RuC8H8]+ the

report

solution

solution,%~m of a small on

chloride

was

(II) ion

of

= 374 smount

in aqueous occurred

more

soluble

(II) was S cm2

in water

highly

mol-1).

than

[ CRu-

conducting

(eg.

Unfortunately

of CsCl,

together

solution

indicated

meant

that

no firm

with that

the

the fact

extensive

conclusion

about

123 electrolyte The 6 n _C6H6 two

type

could

1Ii nmr

spectrum

resonance

have

benzene

very

and

likely

an aqua to the

t0 either

complex

the

and

slow

for

synthesising

ment

of

diene

[lo].

- anions

* Zelonka

and

[l]

and

6.036

chemical

shifts

given

chemical

shifts

are

they

explanation ordinated when

are with comes

n6-C6H6

from

the

chemical is very

(0.116)

and

was

C5H5N,

resonance

'H nmr

of the

the

with

internal

TMS

respect

complex

large

Unfortunately.

resonance,

occurred.

a good of

the

displace-

unknown

excess

fac-

of various

for [ {Ru(C,II~)C~~]~]

fact

work

and

that

these

whereas SupPort

observed

for

the

in for

this

the

co-

of [Ru(C6H6)C12(phle2Ph)] capillary

Also,

the

q6-C 6 H 6 resonances

Th!S lock

aqua

(II),

via

the

lock.

spectrum

(5.356). two

etc)

their

frequency

reference

6 n -C6H6

to be

the

to

to higher

TM.5 capillary

to an external

'IRS reference

similar

of

also

with

of these

to suppress

complexes

le2S

TMS

previous

is due

this

new

shown

from

shoved

and by

(II).

positions

arises

to high

in the

shifts

any

between

to an internal

respect

of

to synthesise

discrepancy

shift

ion,

of anionic

to an external

resonance

berween

in D20

the

in D20

shifted

obscuring

range

probably

respect

(II)

of 1 {Ru
the

The

above

in CDCl with 6 to an internal

reference

and

of Cs[Ru(C6H6)C13]

relative

opposed

C12j21

run

intense

D30

It is therefore

spectrum

solution

however,

quoted _

.*

D30

thus

of one

below),

IH nmr

single

[~u(~,~,)Ci(~20)21+

for

(see

a

which

In an attempt

the

(L = AsPh3.

Attempts,

Baird

at 5.93

ref [l]

more

a wide

by reaction

6.5O(w)6

chloride

bases,

to the

precipitation

Ph3PhCH2P[Ru(CO)C13L2]

in D20

added

to 5.90&),

type

tRuC13L3]

of

of in

to a combination

observed

obtain

became

5.20

and

complexes

Ph3(PhCH2)P[Ru(CO)C13
Earlier, precursor

peak

(from

furthermore,

and

consisted

[ Ru(C6H6)C13D30][3]

Lewis

measurements.

[bu(C6H6)C1&

]Ru(C6H6)C12(D30)].

were

water

of

or

at 6.406

with

process

of CsCl/HCl

frequencies

(II)

in D20

aqua

by displacement

neutral

dissociation

residual

signal

of

conductivity

at 6.39(vs)

the

complex

formed

reactions

amounts the

the

these

that

2+ respectively

neutral

that

is probably this

the

whereas

.resonances

assigned

and [ Ru(C6H6)(D30)3] cations

from

of Cs$Ru
at 6.406

coordinated

workers

be drawn

to both (0.106).

the

(5.956) difference of

[ ifh(C6H6)-

external

TMS

as

_

124 L gave

only

(II) with orange with

and

excess

solid

1

8.36

latter

(C5H5N)

(reported and

this

In contrast,

synthesising

were

dependent

the

monomeric

(PR3

was

under

resulted

in loss

previously

= PPh3,

reflux

on

PMe2Ph,

the

and

at -ca.

5.906.

resonance

of

at

7.3

The

5.936)

with (II)

either

excess

in neat

the well-known

(II) was

excess

light

(II) the

ring

of PMe2Ph

either

petroleum

by

by

Me2SO

in

pyridine

[ll]

trans-

[RuCl,(PPh,)$

%uC13xR20"

with

excess

although

the

as it represents

the

gave

or with

anionic

phosphines For

example,

with

[RuC12(PPh3)3]

mer_[RuC13(PMe2ph)3] rearranged

(II) with

prepared [13]

[Ru(C6H6)-

ci~-[RuC19(PMe9Ph)~],

PMe2Ph

readily

CdRu(C6H6)C13] first

.

[l-3]

methanol.

tertiary

of excess

of PPh 3 in methanol

PR3

reported

SbPh 3 in

with

refluxing

the

excess

Cs[Ru(C6H6)C13]

. previously

complex

and

Similarly,

excess

In CHoCl ci~~RuCl~(PYe~Ph)~] J 2'-

gave

with

formed.

in methanol

(bp 60 - 83OC)

tertiary

conditions

reaction from

and

previously

and

reaction

In contrast,

(II)

shaken

the

were

shaking

in methanol

in so much

H nmr

reaction

PMePh2)

benzene

[ Ru9C13(PMaPPh)6]C1[12].

Hence,

and

The

[Ru(C6H6)C12
of compound

if

conditions.

synthesised

IX?].

1

and

reaction

by

of the

(II) with

in degassed

at 5.65

refluxing

Thus,

prepared

However,

refluxing

resonances

the

precipitation

d6-Me,SO

[Ru(C6H6)C12(?dezS0)],

complexes[Ru(C6H6)C19
C12(SbPh3)]

by

broad

or Cs[Ru(C6H6)C13]

both

the phosphine.

in methanol

followed

and

from

of

refluxing

solution,

except

complex

an n6-C6H6

prolonged

products

phosphines

a yellow

solvents

resonances

d6-Xe2SQ

or gently

for [Ru,(C~H~)C~~(C~H~N)].

showed

of [Ru(C6R6)C12(C5H5N)]

] RuC12(C5R5N)4]

hexane

solvent

to have by

closely

&C6H6

to the

verified

a mixture

nature

two

gave

deuterated

[Ru(C,H~)C~,
methanol.

The

in most

plus

assigned

was

very

i- this

in ref [l]

refluxing

gave

insoluble

shaking

by concentration

this

analysed

spectrum

was

from

either

Thus,

in methanol

of pyridine

ether

was

H nmr

complexes.

isolated

diethyl

compound its

neutral

by

excess

to PPh3

refluxing

. is in itself

arene

complex

of interest

of ruthenium,

in

125 the

lability

of the

that

of

from

[ Ru
and

the

diene

therefore,

rather

than

occurs

little

the

slowly

only

24h

[14]

less

loss

of

the

than ion

C6HS

ring anion

the [Ru
material.

Thus,

in high

analysed

quite

reaction

occurred

an orange

.

however,

In our

hands,

(ca _-

12%)

experimental

(IIIa)

yield

from

a similar the

reaction

dark

a dark

absence

of

NH

this

reaction

plus,

on one

Since

for

],I with

(III)

has

[{Ru
excess

(IIIb).

6

by

[Rh2C13
in

of NH PF for 4 6

orange-yellow

PF

4

identified

shown

route

red-brown

a slight

which

of [{3hC12
preparative

with

< >90$)

with

of

from

solid

section)

is isoelectronic

for [Ru~
in the

of

reaction

solution

an orange

temperature

well

gave

in _ca 4OT, yield,

stirring

yield.

[3 ] , the

Smith

[Ru(NH~)~
in high [15],

and

water

(see

to be

at ambient

gave,

than

by using

much

loss of chloride

Thus,

starting

yields

cation

isolated

examined.


product

in methanol

methanol

hot

variable

[Ru2(C6HS)2C13]+

NaBPh4 been

low

a further

was

is very

readily

gained

as a

precipitated

analysis

which

.

more

by Bennett

]
as I RU,UZ,H~)~C~~I PF~

X-ray

much

is to be

earlier

[{Ru
occasion,

group

of [C_H_RuC13RuCcH6~

As reported

produced

benzene

in [Ru(CO)C13(C,HS)]-

[CRu
b) Synthesis

NH4PF6

coordinated

solid No

which

apparent

or if methanol

was

replaced

by acetone. The and

mull

ir Spectrum

of



confirmed

the

presence

in the far ir spectrum two intense bands at 276, 264 cm

observed, indicative of bridging u(RuC1) vibrations J(RuC1) of (IIIa) quoted at 265 cm-l).

of PF 6

-1

were

(cf in ref [3], -

Compound (IIIb) gave conducting

solutions in MeNO, with values characteristic of 1:l electrolytes il6j
-3

0

mol dm -.I- Vs c-

-3

solution,&

C' plots

over

m

= 82 S cm2 mol-l) and this was

a range

of concentrations

had a slope characteristic of 1:l electrolytes

which

(see experimental section).

The 'Ii and 13C-jlH 1 nmr spectra of (IIIb) in d3-MeNO

2

at ambient

126 temperature

both

at 5.90s

and

remained

intact

92.0

However, 6

rl-C6E6

section

resonance

for

indicating

that

the the

dimeric

unit

solvent.

observed. 6 VC6R6

_two

indicating

Thus,

the

resonances

resonance

positions

[CRu(C6H6)C12}2]

facile

at 6.35 are

dissolved

'Ii nmr

and

and

has

6.506

occurred

(IIIa

or b)

comparable

identical

[6.39

cleavage

of

6.48Stof

virtually

in D20

bridge

spectrum

to those -

see

as shown

in

equation.

--.\ c

1+

.Cl

($Ru~~~lvent -1

/

+

three

at 5.95i
to the quoted

singlets 6.15(w)

positions


of

[Ru(C6R6)(d6-Me2SO)312+ signals

suggested

to give

the

and

the

6.5O(s)5

in the which

The

ClJ.

monocation

has

H nmr

spectrum

corresponded for

the

[Ru
(6.476)

that

observed

-F?J

/

n6-C 6 A 6 resonances

the


were

F

Solvent

Cl

1

(IIIb)

\ Cl-‘Ru

\

Cl

In d6-Me2S0.

7

Solvent

Solvent ,_.'1

I)t-R+l>Ru

of

n6-C 6 R 6 groups

other solvents such as D20 and d6-MeaSO, more than one

These

a)]

sharp

respectively.

was

contained

for

a single

in this in

intensity.

the

ppm

resonance

in D20

found

showed

species

<6.126)

relative reacted

closely

and

intensities further

with

[ Ru-

of these d6-Xe2S0

dication. +

As discussed cations,

(L = PR3.

formation weakly the

solvated

was

due

signal

formed

As

to the

for

the

P(OR)2Ph), is by

closely

related

the most

likely

intermolecular

[Ru
in ref [3],

reported.

is probably one

P(OR)Ph2,

monomers

being

' Interestingly

only

[17]

of [ Ru~(C~R~)~C~~]+

monomers

6.045

elsewhere

only

discussed different

for QIIa)

in ref

earlier, references

mechanism

coupling

of

of the

and [Ru
of [{Ru(C~H~)C~~}~I

a single

fRu2C13LJ

resonance the

for

difference

used

[ 31 is puzzling.

but

with

either

(IIIa)

in D20

in chemical

the observation

at shift of

127

r

(1) ! 1

solvent

I

a

/

s\

I

R” /-”

R”\

Cl-'lhLCIA c

or hot

chloride

bridged

earlier the

work

*

water.

These

cation

with

double

to obtain although, readily

the

AH nmr

formed

there in DSO

then or on

couple

to give

the basis

chloride which

for

then

rearranges

the

formation

doubt

d6-MeSSO.

that

from

complexes

solvated

of [{Ru
is no and

bridged

the triple

of evidence

ethyldiphenylphosphinite

solubility

evidence

of course,

may

directly,

ruthenium

cationic,

Unfortunately.

are

_?

‘.solvent 4

C1RuC13Ru(solvent)(CgHs)lf

*

PF6


methanol

via

-‘-

,yCIL A/

[17],

intermediate

readily

to

(III)

in methanol

of methanolate analogous

[
is too

monomers

momomeric

species

low

128

The

low

solubility

methanol

six

strong

ccmbination


1-s SCN-) hcwever

bonds

of these

Attempts

neture

of

these

appreciable

Reactions

displacement

of

the

refluxing

24h

deposited

for

to the

hoped

in methanol

isolated

from

which

high

the

from

very

prevents

(L = C5H5N.

by

with

yield

a gereral

were the

insoluble

formation

facile

of

route

of pyridine

crystalline

to the

On

vi2 the

proved

benzene

nitrogen

greater

thaa Thus,

for -ca 4h

for

the basis

tendency

rings.

in ethanol

under

solid.

preparation

above,

cleavage

coordinated

on standing

of

.MegSO. RCN -etc)

bridge

of the

excess

synthesis

as discussed

However,

which

an orange

NR4PF6

stems

this

prbvide

replacement

solution

x = Br-, = C H 6 6'

arene

being

[RuR-

monomers.

that

might

(III)

cations

Cl ]PF

monomers

to undergo

an orange

(II)

force

bridged

with

compounds

n6-C61i6 groups.

compound

driving

halide

probably

as [RuRC13L6]+

to generate

desire

gave

(C R_) &6*~6

(III)

such

the

[{Ru(arene)X3]3]

failure

it was

of complexes

of ruthenium

; X = Cl-;

H Ye 63 3

of methanolate

of [Ru

desire

triple

[{Ru(arene)XR]g]

[Ru,(CSE6)RC13]PF6

(III)

the

of [{Ru(arene)Xg]g]

This

Originally,

of

other

only

amounts

in either

of [Ru,(C,H~)~C~~]+

presumably

= 1.3,5-C

unsuccessful, mixture_

with

is

to prepzre

+ (arene

salt

intermediates.

by reaction

reaction

PFS-

together

or water,

achieve

Cl

of the

of

a further analytical

. data,

together

formulated of the

with

as the

remaining

%i nmr,

monomeric filtrate

.

replacement

n6-C6H6

reaction 2nd

of

mixture

also

identified brid;e

as

cleavage

between

cation

[Ru
to retain

proved

also

was

best

Concentration

bridges

byfiotolysis only

this

orange-solid

chloride

unsuccessful,

but of

transinduce

the

same

IRu(C~H~)C~(C~H~N)~]PF~

isolated. (III)

[Ru
the

for pyridine

being compound

studies,

the non-conducting

groups

trans-[R~Cl~(C5H5N)~] Reaction

conductivity

gave

Attempts

[ RuClZ(C5R5N)4]

ir and

occurred

and

EtgS

and

[Ru
with

gave

tertiary

two

compounds

phosphines

This 2nd

129 arsines for

when

short

unknown (PR2

ras

reaction

shaken

times

cationic

tertiary

The

(III)

(III)

produced

with

and

of

loss

excess

bridged

gave

this

from

a yellow

cation

(III)

was

synthetic Recent

itself

with

route

triple

In view

of PR2

[19],

ability

of

of

this,

by

with

the

excess

triple

of PMe2Ph

chloride

As discussed

rearrangement cleavage

and

earlier

reactions -~-C6R6

of [RU~(C~H~)~C~~]PF~

of new

chloride

reaction

q6-C6R6

cationic

compounds

that

similar

facile

bridged

complexes.

undergo

this


displace-

attack

do not

bridged give

cleavage

reactions

example,

of P(OR)Ph

2

a convenient [Ru
of type

For

cations

occur

reaction

(R = Ne.Et)

Microanalyses

4000-250

were

that

the

closely

cleavage

may

be a result

PR2

groups

which of

on the

ring

by B.M.A.C.

and

Department.Infrared cm

-1

on a Perkin

spectra Elmer

457

of

in benzene

of

related

[ Ru2C12-

reactions

with

strong

electron

the

inhibits

bridge

[Ru
excess donating

cleavage compounds

[l]).

Experimental

Chemistry

of

and [RuC12
bridge

inertness

does

bridge

excess

it is surprising

coordinated

nucleophilic

triple

cleavage

do not

although

nucleophiles

towards

only

refluxing

of [Ru
isolated.

by bridge

of [Ru
the

which

conditions

example,

(III)

bridge

chloride

cations

(PR9)6] +

reflux

a mixture

formed

reactions


a mixture

other

facile

shown

[Ru2YC14
likely

synthesis

to new

has

other

For

refluxing

formed

although

to the

the

work

most

groups.

was

previously

[Ru(C~H~)CI(PR~)~]PF~

under

from

ligand

by PMe2Ph.

a route

[Ru2C12L6]+.

solution

of the

to the

of PR2

gave

[Ru2C13
In conclusion, provide

-C6A6

In contrast,

cis-[RuC12
6

excess

a route

complexes

excess

the 7

with

provided

of PPh 2 in methanol

complex

[ 12,171.

with

of

iRuCf2
in methanol

this

phosphine

PMePh2).

reaction

in methanol

and

= PPh 2, P?de2Ph,

sometimes

PF6

(III)

the

were grating

University recorded

of Edinburgh

in the

spectrometer

region

using

Nujol

by

PF6.

130 and

hexachlorobutadiene

region

400-200

using

pressed

on Varian nmr

-1

polythene

on

chemical

a Varian

ionic

charges

stage

microscope

and

are

720

plates

far

points

obtained

13C-{lH]

and

at 25.2

frequency

of

using

310

Portland

[17],plots

is a function

determined

MRz

SillIe4).

a model

earlier

slope

were

were

operating

at 2985

whose

in the

spectrometer

ir

spectrometers

As described

line

and

spectra

to high

made

bridge.

Belting

[20].

m-360

in ppm

a straight

C

IR

spectrometer

were

conductivity

"i vs c* gave

and

quoted

iodide

Hydrogen-lnmr

XL100

measurements

Electronics

RIIC

discs.

HA-100

shifts

Conductivity

on caesium

on a Beckman

Associates

spectra

(13C

dLo-

cm

mulls

with

of

of

the

a Kofler

hot-

uncorrected.

Materials Ruthenium ammonium caesium

trichloride

hexafluorophosphate

methane,

pyridine,

(Hopkins

and

and

were

in Table

and

are

degassed

solvents 1L

conductivity

listed

for

under

mercury

each

data nmr

data

an atmosphere

U.V.

lamp

was

used

caesium 5 days.

mmol)

chloride The

was

shaken

(0.4Og)

resulting

and orange

are

in ethanol concentrated suspension

for

from

I, SCN) with

were

and "RuCl

3

xH 0' 2

compounds in Table

reactions

were

the

and

with

hydrochloric decanted

of LiX. are Diagnostic

2.

carried

a medium

photochemical

compound

(25 cm3)

prepared

an excess

listed

The

was

dimethylsulphoxide

[1,3]

various

of nitrogen

Caesium(benzene)(trichloro)ruthenate(II)r (0.2Og.O.40

the

All

compound_

nitro-

or 1,3,5-trimethylcyclohexa-

(X = Br,

for

(B.D.H.);

[{Ru(C~H~)C~~]~]

of [{Ru
1 and Hydrogen-l

ir bands

Banovia

[{Ru(C6H6)X2]2]

solutions

(Fisons);

earlier

diene)

Ltd);

(Maybridge):

(Kodak).

as described

Emanuel

tetraphenylborate

nesitylene

(or cyclohexa-1.4

aqueous

Analytical

and

prepared

respectively_

(Ralph

sodium

triphenylstibine

Williams);

cyclohexa-1,3-diene

by treating

triphenylarsine and

cyclohexa-1,3-diene,

Matthey);

dimethylphenylphosphine

acetonitrile

[{Ru(C6H3BeJC12]2]

1,4-diene

and

(Yohnson

triphenylphosphine

chloride,

methgldiphenylphosphine

given

hydrate

out

pressurei reaction_

[{Ru(c,H~)c~~)~] an excess acid off

of

(5 cm=)

and

washed

for

in

131 TABLE1 Analytical

and

Conductivity

Data for some _-----__ Found

Compound

C

Ii

n6-Areneruthenium
Complexes

Calculated -

N

Cl

C

B

I

-Cl

N

Cd Ru
16.9

1.4

-

25.2

17.2

1.4

-

25.5

[Ruu~~H~)c~~(c~~N)I

40.4

3.3

4.6

-

40.1

3.3

4.3

-

]Ru
56.6

4.3

-

56.3

4.1

-

-

[R~
49.9

4.1

-

50.7

4.2-

[Ru
28.8

3.6

-

29.2

3.2

-

-

[ RuC12(PMepPh)4]

52.4

6.1

-

53.0

6.1

-

-

3Q.0C

[Ru2(C6R6)2C13JPFB

23.8

1.9

-

23.6

1.9

-

17.4

82.0

37.0

3.0

5.3

37.1

3.1

5.4

-

84.0

[Ru
34.9

4.6

-

35.3

4.7

-

-

[nu
31.5

4.6

-

31.2

4.8

-

-

64.0

[Ru
56.7

4.2

-

57.1

4.1

-

-

78.0

[Ru
51.6

3.7

-

51.9

3.7-

-

75.0

[Ru(C6Hg)C1(PMe2Ph)2]PF6

41.3

4.4

-

41.5

4.4

-

-

72.0

[Ru(C6H6)C1
50.5

4.8

-

50.6

4.2

-

-

67.0

[ RuZC13(PMe2Ph)6]PF6

44.9

5.1

-

44.9

5.2

-

-

74.0

16.3

2.9

7.1

16.1

3.0

7.3

-

[Ru(C6H6)C1(C5H5N)2]

PF6

[ Ru

16.2

37.4b

-

NH4PF6

-_. a

Equivalent

stated) at 10 CH2C12

with

-. conductivities -3

no1

dm

-3

- rearrangesto

methanol

v(RuC1)

280

and

(S cm2

(1.0

cm3)

addition 86%)

mmol)

cm

was

for -ca 4h. of diethyl

v(RuC1)

280

) measured b

in nitromethane

measured

in I-I20

(decomp)

(Yield


c measured

[Ru2C13(PKe2Ph)6]C1.

-1

Benzene(dichloro)pyridine
-1

concentration

diethyl

(broad)

mol

ether

mp.

ruthenium(I1): shaken

ether

0.31g.95%)

.

in methanol

Concentration

cm-l.

270°C

gave

The

(10 cm3)

of the

an orange

compound with

resulting

solid

mp.

Cs[Ru(CGH6)C13] excess

yellow 245OC

of pyridine solution

(decomp)

and

(O.O7g,

in

132 TABLR

2

Hydrogen-l

umr

data

for

some

n6-Areneruthaaium
Complexes S"Ppm

Compound

Solvent

]{Ru
D20a

6.39=;6.50=

Ca[ RU
D20b

6.40=

[

~
[ FWC6H6)C12PPh3]

---

resouaacea

5.65.5.90'

7.30,8.80
-13

5.90

-ca 2.70
cDC13

5.40

7.50

5.40

7.65
d6-Me2S0

[Ru
--___ other

n6-C6H6



[RuC1,
cDC13

[Ru
cDC13

5.35

CDClb 3

5.95

CDCl3

5.68

JpR 7.40-7.70
cDC13

5.50

7.40-7.60
CDC13

5.70

2.90
d3-#"NO2

5.90 6.35=,6.48=

D2°

d


specified,

external

TMS

d From


d6-Me2C0

6.16

CDC13

5.95

cDC13

5.52

7.30
CDcl

5.75

7.20-7_60

CDC13

5.87

7.50
CDC13

5.66

7.40-7.60
3

7.45,8.00,8.85

1.60(t)

q
c

[Ru]

12.OHz)

5.95c,6.15c,6.50c

reference

capillary.

12.OHa)

d6-Me2S0

t
a Unless

12.0Xx)

See

is TMS
for

lock)

assignment

b With of

these

respect

to

resonances


133 Benzene(dichloro)triphenylphosphine Cl31

(O-log;

0.23

in methanol

mmol)

was

ruthenium(I1):

shaken

for -ca 3h to give

(O.llg.9l$)v(RuC1)

295.

280

with

a dark

excess

red

u
ruthenium(I1)

mp.

290,

cm

-1

v(RuC1)

78%)

v(RuC1) mp.

200,

272

cm

mp.

were

similarly

275

cm

-1

Ii )C13] 66

PMe2Ph

(0.50

gave 241

(O-log;

cm3)

a yellow,

0.23

6h.

y(RuC1)

was

ruthenium(I1)

refluxed

resulting

solid

290, mp.

211°C

prepared.

mmol)

The

crystalline

mp.

in methanol

yellow

126OC

The

solution

compound excess

with

on standing

(0_13g- 2 82%)

v(RuC1)

288,

cm-'_

Tri-n-chlorobis[


The

complex

with

water

with

a saturated

orange mp.

for

182OC

; benzene-

Cis-dichlorotetrakis
mmol)

alp. 197Oc

220-222OC

and benzene(dicbloro)dimethylsulphoxide 291,

solid

0.40

benzene
ruthenium(I1)

-1

(O-log;

ruthenium(I1):

cm-';

(0.07g;

(dichloro)triphenylstibine 269

Cs[Ru(C6H6)-

cm-l.

270

175OC

compound

of PPh3

crystalline

Benzene(dichloro)methyldiphenylphosphine (O.O9g,82%)

The

(10 cm3)

was

(decomp)

another

characterised
285

by cm

prepare

this

latter

methanol

455

(25 cm3)

solid

diethyl

mp.

Conductivity

On leaving solid

[14]

3250,

).

3320.

excess

filtrate

and days

treated the

and

methanol

for

another

which

cm-';

&NH)

was

subsequent

1615, attempts

0.40

mmol)

1.00

mmol)

and washed

with

water,

280°C

(decomp)

(0.22g;

slope

water

(0.16g;

off

for IRu2C13
several

deposited

(0.2Og;

filtered

at 298K.

filtered

reflux

1630

cm-';

to

unsuccessful.

of NH4PF6

2

the

3370

Unfortunately, were

with

under

A:

as [Ru(NH~)~(C~H~)C~]~(PF~)~.NH~PF~

was

in MeNO

was

heated

was

After

and washed

[{Ru(C6H6)C12]2]

with

orange-yellow ether

cm

-1

compound

complex

off

was

solution

of NH PF 4 6‘

12%).

3180,

0.40 mmol)

orange

solution

analysis

; V(NH)

440,

The

crystalline

X-ray

421,

B: The

2h.

filtered

orange

-1

(0.20s;

(0.03g;

w
Method

for

aqueous

precipitate

255OC

7 days,

[{Ru(C6H6)C12],]

Method

Slope = 190.

of

9a)

A0 -

v
was

264,

vs C3 plot

13C-{1H]nmr

stirred

for

in

24h.

The

methanol

and

276

cm-l.

= 207;

in d3-bieN02

at 303K.

134 82.0

and

The

compound

soluble

in

pp!n
very

sparingly

is

insoluble

in

CHCl

acetone.

Benzene(chloro)bis(pyridine)ruthenium(II)hexafluorophosphate: [Ru2(C6R6)2Cl3]pF6 with

24h

pyridine

gave

285

cm

orange

CO.40

a yellow

-1

solid


cn3)

for

mmol)

-ca

crystalline

Concentration

_

0.14

(0.09g;

was

6h.

The

solid

of the

refluxed yellow

mp.

24%)

solution

from

v(RnC1)

338

cm

(0.20 by

(O-log; cm8)

265

cm

-1

crystalline

The

of solvent

recrystallised

283,

mmol)

for -ca 3h.

evaporation

was

0.16

)_

from The

solid

complex cm3)

standing

66%)

reaction

for

w(RuC1)

gave mp.

an

255OC

(decomp)

.

was

The

refluxed

orange under

in ethanol

solution

vacua.

The

acetone/diethyl

filtrate

frzm

on standing

for

was

orange

ether

the 24h

above

complex

mp.

with

and

225OC

Et2S-

concentrated

precipitate

reaction

identified

[Ru~(C~H~)~-

(30 cm3)

filtered

obtained

(decomp)

gave

v(RuC1)

an orange

as benzene(chloro)bis-

(diethylsulphide)ruthenium(II)hexafluoraphosphate 290

(30

OP

(0.05g;

this

Benzenedichloro(diethylsulphide)ruthenium(II): C18]PF6

in ethanol

227-22S°C

filtrate

The

trans-dichlorotetrakis(pyridine)ruthenium(II) -1

benzene

CH2‘+,

3'

mp.

175OC,

w(RuC1)

cm-l.

Benzenechlorobis(triphenylphosnhine)ruthenium(II)hexafluorophosphate: -. The

complex

(20 cm3) was

[R~~(C~ll~)~Cl~]l?.

with

filtered

hexane

and

and

hexane

mp.

172OC

yellow

excess off

identified to the (O.llg.

solids

phosphate

from

mp.

of PPh3 the

:0.2Og;

=

(O.ZOg;

yellow

0.32

0.80

mmol).

solutioc,

yellow 41%).

filtrate w(RuC1)

gave 290

the

cm-l_

was

shaken

The

red

recrystallised

as [Ru
Addition

precipitate from

CB2C12/

of diethylether

yellow

crystalline

Similar

reactions

142OC,

w(RuC1)

310

cm

-1

;

product gave

the

benaenechlorobis
158OC'

URuCl)

benzenechlorobis(dimethylphenylphosphine)ruthenium(II)hexafluoro-

phosphate

in methanol

benzenechlorobis
phosphine)ruthenium(II)hexafluorophosphate and

mmol)

mp.209-211°C,

v(RuC1)

298

cm

-1

.

292

cm

-1

135 Tri-~-chlorobis[tris(dimethylphenylphosphine)ruthenium(II)]hexafluorophosphate: The

compound

(20 cm3)

[RuZ(C6H6)ZC13]PF6

with

to the

yellow

(0.37g.

92%).

excess

(0.2Og;

of PMe2Ph

solution

(1 cm3)

gave

a yellow

Ltd.

0.32 for

mmol)

5h.

was

refluxed

Addition

crystalline

solid

in methanol

of diethyl mp.

ether

238-239OC

Acknowledgements We

thank

Johnson

Matthey

the SRC

(DRR)

and

University

and

Dr.

A.S.F.

the

Boyd

and Mr.

for

loans

of

ruthenium

of Edinburgh(TA)

J.R.A.

Pillar

for

Baird,

Canad.

J. C+.

for

trichloride,

financial 13

running

support 1

C and

I

H nmr

spectra.

References 1.

R.A.

Zelonka

2.

ibid,

3.

B.A. 233.

4.

A.S. Ivanov. Ser Ebim, 4

J.

and

B.C.

Organometal

Bennett

and

A.K.

A.Z.

Smith,

Rubezhov

(1974)

44 (1972) _

383.

J. Chem.

Sot.

and

S.P.

and

6.

H- Brunner and R-G. Gastinger, J.C.S. J. Organometal Chem., 145 (1978) 365.

7.

R.H. 325.

8.

Preliminary Communication, J. Organometal Chem., 116

9.

T-A. Stephenson, E.S. Switkes Dalton Trans., '1973.2112.

Abel,

M.C.

and

L. Ruiz-Ramirez <1974__1640.

Baird,

A.J.

J.

and

(1974)

Trans. --*

Acad.

Nauk.

Stephenson,

P.W. Armit. A.S.F. Boyd Trans.. (1975) 1663.

13.

T.A. Stephenson (1966) 945.

14.

R-0. Gould, C.L. Jones, D.R. Robertson Cryst. Struct. Comm., 3 (1978) 27.

15.

J.W.

and

and G. Wilkinson,

P.M.

Maitlis.

Comm..

(1977)

Chem.,

and T.A.

J. Chem.

G. Wilkinson,

and T.A.

127

L. Ruiz-Ramirez,

12.

Bennett

Chem.

D.R. Robertson (1976) C29.

E.W.

and

3063

Chem.,

Organometal

11.

Kang

Izv.

J. Organometal

Pearman,

and T.A.

M-A.

Dalton

Gubin,

D.F.

Crabtree

(1972)

S.S.S.R.

931.

5.

10.

Dersnab

fhem..

50 _

J.

Inorg.

and

J. Organometal

Sot.

141

Dalton

(1977)

Sot.

Trans.,

Sot__, (1959)

Nuclear

Chem.,

ibid

Stephenson,

J. Chem.

T.A.

C55

488;

J. Chem.

J. Chem.

Stephenson,

(1977)

Sot.

Chem.,

Dalton

-28

Stephenson,

-30

(1971)

3178.

127.

136 16.

See

W.J.

Geary,

17.

W.J.Sime submitted

and for

18.

W.J. Sime submitted

and T.A. Stephenson, for publication.

19.

J. Chatt.

B.L.

20.

R-D.

Feltham

Coord.

Chem.

T.A. Stephenson, publication.

Shaw

and

and

R-G.

A.E.

Hayter,

Reviews,

x

(1971)

J. Organometal

J. Chem.

Field,

Sec.

J. Chem.

J. Chem.

Sot..

81. Chem

Dalton

Sot., (1964)

,

Trans..

(1964) 4587.

3466