Selective synthesis of mono-alkyldichlorosilanes via the reaction of olefins with dichlorosilane catalyzed by group VIII metal phosphine complexes

Cl

Journal ojfkgcnometaliic Chemistry, 0 Ekevier Sequoia S.A., Lausanne -

Prelininary

communication

SELECTIVE OF

SYNTHESIS

OLEFINS

PHOSPHIWE

Hamao

160 (1978) Cl-C7 Printed in The Netherlands

WITH

OF

MONO-ALKYLDICHLOROSILANES

DICHLOROSILANS

CATALYZED

GROUP

THE

VIII

REACTION

METAL

COMPLEXES

Aoki,

Noritaka

Department of Chemistry, Gunma

---ii-v,

and

BY

VIA

Watanabe*,

Yoichiro

Masafumi

Sakurai,

Ken-ichi

Watanabe

Nagai

Kiryu, Gunma 376 (Japan)

(Received July llth, 1978)

Summary In

the

phosphine were

hydrosilylation

complexes

found

to

be

exclusively. be

the

e-g-r etc.

been

olefins.

metals,

catalysts,

giving

and

and

effective

peroxide,

Recently, [3],

shown

to

many

dichlorosilane,

Ni,

Ru,

Rh,

Pd

and

Pt,

n-hexyldichlorosilane was

catalyst

However,

the

for

the

of

hydrosilylation

effective

tributylamine,

Group

palladium be

of

a variety

Chloroplatinic

r21 I rhodium have

VIII

investigations out

benzoyl

catalyst.

with

found

to

selective

of mono-organodichlorosilanes.

carried

111.

active

convenient

Extensive been

Group

l-hexene

Tris(triphenylphosphine)chlororhodium

most

synthesis

of

of

acid VIII

[4],

effective

hydosilylation

catalysts

platinum,

is by

far

the

catalysts

most

with

has

been

commonly

complexes

[4a,5] for

olefins

the

and

acid,

used of

iridium

nickel [4a]

hydrosilylation

dichlorosilane

have found,

chloroplatinic

metal-phosphine platinum

of

of

(H2SiC12) in

c2

the

presence

palladium

of

these

complex are

of

hydrosilane.

terminal

available

olefins

on

tion

of

nally

and

substituted

one

with

case and

of

catalyzed

reported

that

hydrosilylation

gave

a mixture

also

H2SiC12

reported gives

monoalkyldichlorosilane

mono-

[7]

(eq.

the

a mixture 183

few

reaction

of

that

a

only

acid

dialkyldichlorosilanes

co-worker

olefins

for

attention

chloroplatinic it was

[6] or

Benkeser internal

the

little

dichlorosilane

alkyldichlorosilanes Recently,

received

Thus,

with

except

complexes,

has

[4bj,

reports this

metal

of and

di-

1).

hydrosilyla-

of

two

inter-

2).

(eq.

R2SiC12 RCH=CHZ

RCH2CH2SiHC12

T

t

(RCH2CH2)2SiC12

(1)

H2PtC16

H2SiC12

*

RCH=CHR'

Reactions provide are

a convenient

converted Si-H

cious

choice Ru,

or

Rh,

excellent lane

to

organosilicon

great

importance,

Pd

and by

Pt), the

conditions find

out

and,

We

by now

complexes

also,

(eq. an

they

report of

Group

of

can

olefins

can

of

that

using

be

either

with

VIII be

may

which

they

reactions

monoalkyldichlorosilanes

hydrosilyldtion

since

organodichlorosilanes

compounds

.ii-Cl functions.

triphenylphosphine

to

of

various

of

mild

order

are

SiHC12

alkylhydropolysiloxanes

their

yield

under In

of

type

route

to other

their

(Ni,

this

(2)

R:HCH2R ’

SiHC12

of

precursors

-I-

RCH2CHR ’

H2PtC16

judi-

metals

prepared

in

dichlorosi-

3).

effective

and

convenient

catalyst

for

Catalyst RCH=CH2

eq.

3,

f

the

H2SiC12

catalytic

employing

I-hexene

stainless

steel

*

activities as

bomb

substrate. was

charged

of

RCH2CH2SiHC12

these

complexes

In a typical with

1-hexene

(3)

were

experiment, (54 mmol)

examined a 50 ml and

c3 RhC1(PPh3j3 cooled

(2.39~10-~

in a liquid

(21 mmol, bath),

1.7

was

the

bomb

was

heated

(lmx

4mm

temp.

nitrogen

distilled

into

allowed

at

70"

Teflon

156")

to

(oil

the

used.

A

formed

g-hexyl-

to

relative

then

15

h.

the

at

out

at

-20"

that

elevated

GLC

then it

analysis

545-AW;

the the

di(c-hexyl)-dichlorosilane

and

Subsequently,

cooling,

on

used),

(ice-salt

valve

on Celite

based

silane

Dichlorosilane

inlet

After

showed

yield,

carried

tube

KP-96

mixture 99%

the

temperature.

silicone

in

to

evacuated.

through

room

for

20%

reaction and

and

bomb

bath)

[*I

similar

the

reaction

hexyldichlorosilane

mol%

in a calibrated

warm

column,

of

bath

condensed

ml),

was

0.1

mmol;

column

product

was

dichlorosilane temperature

in

n-

94 and

6%

(12OO) yield,

respectively. Results summarized phosphine

of

hydrosilylations

in Table

1.

complexes

dichlorosilane

in

NiC12(PPh3)2,

It will

tested low

to

more

RuH2(PPh3)4,

under

the

of

ccmplexes

gave

alkyldichlorosilane in Table

1 show is

Ph3j3,

the

yields

to

this

is

[6] or

which

1 that to

all

form

gave

Significantly,

use

gave

of

in

the

(rather contrast

to

a mixture

dialkyldichlorosilane

choice

for

the

g-hexyl-

excellent of

two

or

presence than the

di(n-

of mono-

[7,**].

of

chloroplaand

The

tris(triphenylphosphine)chlororhodium,

catalyst

the

RuH3(PPh3J3[Si(OMe)2Pt(PPh3)4

sharp

are

In particular,

(19-99%).

dichlorosilane

in

complexes

active

and

employed.

reactions

that

Table

z-hexyldichlorosilane

and

acid-catalyzed

from

other

catalytically

RhC1(PPh3)3

olefin

only

hexyl)dichlorosilane) tinic

,I,

the

seen

by

RuHC1(PPh3)3(PhMe),

conditions

equivalents

these

were

be

excellent

Phl , _RuH3(PPh3)3[Si(OMe) results

catalyzed

di-

results RhCl(PAcc-

mono-hydrosilylation.

(Continued on p_ C6) *Identification

was

spectra

comparison

and

the

accomplished of

in the

the

usual

physical

manner

data

(NMR

with

and

IR

literature

values. **In

our

from

H2SiC12

effected

experiment,

in

and

preparation

olefins

excellent

in

yield.

the

of

dialkyldichorosilanes

presence

of

H2PtC16

directly

catalyst

was

9 10 11 12

RhC1(PPh3)3 RhH(PPh3)4 RhCliCO)(PPh3)3 RhH(C0)(PPh3)3

4

time,

25 h.

correction

silane

‘Reaction

to the

0

eCatalyst,

standard

(mmol); reaction b GLC yield based

99

19

46

59

99

96

91

85

68

98

with an internal d See ref. 9.

used,

H2SiC12=23-35:10-15

ductivity

relative

al-Hexene:

Pt (PPh3)

0

13c

?

RuHC1(PPh,),(PhMe)d

Pd0'Ph3)4 Pdc12(PPh3)2

4

RuH2(PPh3)4

c;

2c 3c,e

RuC12(PPh3)3 d RuHCl(PPh3)3(PhH)

1

0.2

mol% used and thermal

0 .l

II

1

conwas made; R= ;-C6H13, f mol%, Reaction temp., 170”.

silane

15 h; catalyst, (;-C13H28)

on the

time,

34

21 22f

42

26

92

96

94

99

96

20

19

la

11

16

15

14

RSiHC12 R2SiC12

Run

RSiHC12 R2SiC12

Run

yield (%)b Reaction temp., 120"

and

Reaction temp., 70°

NiC12(PPh3)2

Catalyst

Product

AND Pt-TRIPHENYLPHOSPHINECOMPLEXESa

HYDROSILYLATIONOF l-HEXENE WITH DICHLOROSILANECATALYZED BY Ni-,.Ru-, Rh-, Pd-

Table 1 B

2

a5

50

54

68

53

55

l-Hexene

cycle-Hexene

l-Octene

1-Dodecene

l-Octadecene

Styrene

I,

44

1, 96

II I,

B

o.05g

0.005

0.1

A

53

Ug

0.1

II

I,

53

0.19

100

,I

55

0.25

0.05

11

57

II

r,t,

100

II

50

90

140

0

0

1,

B

"

21

100

a0

0,

II

100

110

0.8

0.1

( “Cl

(mol%)b

50

II

50

II

11

32 a5

A

13

(mmol)

Temp.

15

20

I,

15

,I

10

15

35

15

24

25

16

1.5

0-t)

Time

II

9

PhMeCHCH2SiHC12 i .

I,

.9

PhCH2CH2SiHC12 i

;-ClaH37SiHC12

;-C12H25SiHC12

;-CaH17SiHC12

c-C6dllSiHC12

c-CbH13SiHC12

Me2CHCH2SiHC12

;-C4HgSiHC12

Dichlorosilane

78

a7

72h

a0

79

34

70

70

74

WC

Product and yield

e

e

76-81(3)

67-77(3)

.*

100-106(20)

110-112(155)

t.

OC(mm)

B.p.

or solid was formed.

aA: RhC1(PPh3)3, B: H2PtC1606H20/1PrOH. bRelative to the silane used. 'Isolated yield based on the d silane used, Mesitylene (1 ml) was added as solvent for the catalyst, eKnown compound. fMesitylene, 0.5 ml. gRelative to the olefin used. hBased on the olefin used, 'Only polymeric high viscous liquid

II

II

cl-Methylstyrene53

II

50

64f

iso-Butne

II

34d

l-Butene

(mmol)

Catalysta

Olefin

H2SiC12

Conditions

Reactants

CHLOROPLATINIC ACID

HYDROSILYLATIONOF OLEFINS WITH DICHLOROSILANECATALYZED BY TRIS(TRIPHENYLPHOSPHINE)CHLORORHODIUM AND

Table

2

C6 the

ordingly, olefiqs

was

ducts'were usual

90%.

listed NMR

any

olefins more

in Table of

tractable

in

adducts,

-phenylethyl-

sence

of

these

aryl

those

2 show

that

the

the

Rh

The

Rh

of and

catalyst to

complex-catalyzed also

We

Acknowledgement Research

Center,

of

the

Rh

catalyst

are

prothe

comparison

of

literature). as

high of

reactions

as

the of

adducts

presence

these

only.

A

hydrosilylation

of

these

with

compounds acid

hand, gave

formed the

the

70-

styrene di-

only

in-

reactions

corresponding

g-methyl-8_-phenylethyl-dichlorosilane, Hetflejz and

a mixture

be

the

indication

other

of

the

PhCH2CH2SiR3,

effected,

grateful

Sagamihara,

to

Kanagawa

showed

that

in

triethyl-silane

hydrosilylation

could

in

terminal

On

trimethyl-

and

identified

were

chloroplatinic

the

The

the

thus

in the

yield.

form

PhMeCHSiR3

the

reactions of

no

and

obtained

of

from

catalyst.

or

yields

gave

affords

excellent

olefins

cyclohexene,

products

was

presence

in

alkylsilane, The

with

materials.

effected

and

data

presence

polymeric

as

distillation

alkyldichlorosilane

in the

respectively,

complex

analysis,

the

feature

the

Rh

elemental

a-methylstyrene.

chlorosilane

monoalkyldichlorosilanes

the

by

dichlorosilane

striking of

IR and

analysis

with

using

physical

secondary

various

isolated

(NMR, and

of

out

readily

spectral

Results

and

carried

manner

the

of

synthesis

of

an

but

the

Dr.

H.

229,

added

secondary

where

and

R=Me

or

Kono, for

preto

primary

OEt

internal

product

the

[3dl.

olefin,

yield

Sagami

was

low.

Chemical

fruitful

discussions.

References 1

(a.)C. Eaborn,

"Organosilicon

Publications,

London,

A.

G.

MacDiarmid,

Elements,

Vol.

Inc.,

York,

New

ed., 1, The 1968,

1960,

Compounds", p.

45:(b)C.

"Organometallic Bond p.

to

213.

Carbon,

Butterworths Eaborn Compounds Part

I",

and

Scientific R.

of Marcel

W.

the

Bott

in

Group

IV

Dekker,

c7 2

(a)M. W.

Kumada,

Bennett

and

137;(c)K. (d)M.

Y.

Kiso

P.

J.

and

Y.

J.

M.

Umeo,

Orenski,

Yamamoto,

Capka

and

J.

Uramoto

Hetflejg,

Chem.

(1970)

Chem.,

Organometal.

and

M.

Coil.

Kumada,

Czech.

611;

(b)B.

Chem.,

28

(1971)

ibid.,

31

(1971)C9;

Chem.

Comm.,

40

(1975)

Chem.

SOC.,

2073. 3

(a)R. (A)

N.

Haszeldine,

(1968)

son,

J.

Chem. H.

21

Comm.,

Kono,

104

4

Wakao,

R.

(1976)

S.

43;(j)R.

ibid.,

114 J.

16;(b)J.

73

Abstr., Czech. M.

Green,

Stone, (a)A.

J.

F.

Hara

and

40

V.

A.

J.

Organometal. Coil.

(1975)

Czech. 3680;(f)

Lett.,

(1975)

ibid.,

(1975)

985;(h)P.

Organometal.

Y.

J.

Amer.

Nagai,

Barrau

LangovA 420,

Chem.,

ibid., and

J.

111 Satge,

J.

Ponomarenko

and

9767;(c)Midland

Silicones

1009;

123,960

L.

(1976)

1,942,798;

Hetflejs,

Spencer

G. V. Chem.

(1959);

Ltd.,

J.

87

Chem.

Coil.

432.

Proud,

(1959)

Sot.,

Offen.

and

671.

126

Chem.

Ger.

(1976)

U.S.S.R.

R. A.

Wilkin-

Chem.

and

Ohno,

J.

Co,lm.,

21747;(b)idem.,

Nauk

K.

(1975)

Howard,

S.S.S.R.,

Odabashyan,

40

J.

Kpoton,

Harrod,

15497y;(c)J.

Chem.

G. V.

A.

J.

G.

21.

J.C.S.

(1962)

Kumagai

P. Corriu,

Comm.,

56

M.

and

Hetflejx,

Nagai,

Guerin,

M.

str.,

Y.

C.

Ojima,

Osborn

ibid.,

and

_A. K.

Nauk

Akad.

J.

P. Corriu

and

Petrov,

and

Nagai,

J.

D.

Chalk,

Y.

(1970)

Chem.

J.

3190;(e)idem., and

Palsy, J.

A.

and

(1976)

Tsuji,

Rejhon

J.

J.

Kogure

J.

Chalk

D.

787;(c)A.

I. Ojima

C17;(i)I.

(1976)

(a)A.

(1968)

T.

and

Charentenay,

(1975)

Ojima,

Boroni,

Parish

207;(d)J.

40

N.

de

Sot.,

(1970)

189; (g)I. s.

683;(b)F.

Chem.

Chem.,

R. V.

Brit.

and

P.

Odabashyan, Abstr.,

Chem.

53

Abstr.,

869,343

(1961);

G.

A.

Dokl. (1959) 54

(1960)

Chem.

Ab-

1481. T.

S.S.S.R.,

142

Benkeser

and

A.

Zhnavleva

(1961) W.

C.

K.

Ito

604;

and

Chem.

Muench,

J.

A.

D.

Abstr., Amer.

Petrov, 57

Chem.

Dokl.

(1962) Sot.,

Akad.

855. 95

(1973)

286. H. 132

Kono,

N.

(1977)

Wakao, 53

and

the

and

Y.

references

Nagai, cited

J.

Organometal.

therein.

Chem.,