An NMR study of phenyltin trihalides and their interactions with Lewis bases

INORG. NUCL. CHEM. LETTERS Vol. 9, pp. 1211-1217, 1973. Pergamon Press, Printed in Great Britain.

AN NMR STUDY OF PHENYLTIN TRIHALIDES AND THEIR INTERACTIONS WITH LEWIS BASES Christopher W. Allen, Anne E. Burroughs Ronald G. Anstey

and

Department of Chemistry, University of Vermont Burlington, Vermont 05401 (USA) (Received31Ju~l~3)

The

Chemistry

considerable due to

both the

to

the

numerous

and

bonding

the of

paper

series Lewis

been

compounds

a number

and

of

magnetic

successfully in

alkyltin

done

with

a n nmr

C6HsSnX3(X-C1,Br,I)

(IV)

(1).

of their

a subject This

of

activity

organotin

derivatives

available

for

to

(nmr)

problems

the

and charac-

spectroscopy

relatively aryl

coupling

variation

their

is

concerning

derivatives,

corresponding

study and

been

resonance

applied

the

has

years

techniques

nuclear

we r e p o r t

of

stability

spectroscopic

and

work has

this

variety

widely

structure

In

for

Although

been

little

organotin

interest

terization. has

of

derivatives. constants

in

the

in

presence

bases.

EXPERIMENTAL Syntheses.

Phenyltln trlchlorlde

(2) and trlbromlde

(3) were pre-

pared by redistribution reactions between tetraphenyltln and the appropriate tin (IV) halide and purified by dlstillatlon.

Diffl-

culty in obtaining pure phenyltin trllodlde using standard procedures was observed so it was prepared by applying the boron halide method

(4).

National Science Foundation Undergraduate Research Participant,

1211

1972

1212

AN NMR STUDY

Phenyltln ins a m a g n e t i c

trilodlde.

A i00 ml three

stirrer

48

and

20 ml of carbon

disulfide

dropping

containing

funnel

ide in 20 ml of carbon which

exited

through

solution

was

reaction

which

removed

sta11Ine

product using

slowly

spectrometer

was

bases

recorded

were

Thin iodide

may be obtained

Measurements.

operating added

until

for systems

to metal

ratio

coupling

constants

by column

were

rise

with N 2

trlchloride

to an exothermlc

for 30 mln.

The

solvent

by short

a m~xture

trlchlor-

flushed

indicated

chromatography

was

path dis-

of oily and

to p h e n y l t l n

obtained

at i00 mHz.

cry-

the pres-

trilode.

The pure

on silica

gel

shift was

involving

llgsn

with

more

The product has been liquid forms (5).

amounts

observed The

and

of the

the s p e c t r u m

or the satellltes

tin-proton leveled

with

nmr

coupling

off at a llgand

stronger

donors

the

substantively.

AND D I S C U S S I O N peaks,

satellites

ring.

JNM-MR-100

trihallde

w e a k donors

2:1 while

the ortho,

of the phenyl

a JEOL

Stolchlometrlc

from the noise.

to the main

contain

using

to the p h e n y l t i n

increased

tin trihalldes

protons

giving

in

equallzlng

The p h e n y l t l n

chromatography

in a d d i t i o n

RESULTS

isotopes

was

red oll was purified

layer

trliodlde

of p h e n y l t i n

system

bubbler.

to proceed

approximately

In a d d i t i o n

The

to the flask

no further

indistinguishable

constants

with

contain-

as the eluent.

Spectra

were

a pressure

104-9 °) to yield

product. (IV)

equipped

3 g (Ca 0.01 mol)

was allowed

dlethylether

Lewis

added

flask

of boron

a mercury

(0.3 mmH8,

ence of tin

was

necked

(Ca 0.01 mol)

dlsulflde.

and the r e s u l t l n g

tillatlon

Vol. 9, No. 11

and

the nmr

due

reported

to coupling

in some

The high

spectra

field,

cases

of the meta

ortho

to be isolable

of the phenylSn and

and para,

proton

in both

117

satellites

solid

and

Vol. 9, No. 11

in

ANNMRSTUDY

phenyltin

figure

trichloride

1 consists

of

are

1213

shown in

overlapping

figure

doublets

1.

due

The s p e c t r u m

in

splitting

the

to

of

r

FIG. High Field

ortho

proton

further to

Ortho

by the

split

the

Jom f o l l o w e d

in

below

the

more

for

range

in

phenyltin

table

of

the

agreement

as

each

to

a value

6-9

and

of

for

(6).

tribromide

(J

four

lines

Jom o f

2.7

vicinsl

A similar

while line

protons

to

Hz q u o t e d

species

peaks

set

Trichloride

The o r t h o

para

protons

are

).

Attempts

op

being

phenyltin

then

due

Hz w h i c h

coupling spectrum

to

is

constants is

triiodide

broadening.

o£ JSnCCH r e c o r d e d

with

JSnCCH v a l u e s

direction

the

Phenyltin

obexhibits

The d a t a

may b e

I.

The v a l u e s in

of

in

(Jom).

with

leads

benzene

overlapping

found

proton

spectrum

by Jop

substituted

tained

meta

Satellites

by c o u p l i n g

interpret

far

Proton

1

predicted

previously in

the

published

series

on t h e

for

basis

of of

phenyltin data

phenyltin isovalent

(7).

trichloride

are

The v a r i a t i o n

trihalides

is

hybridization

in

of the

argu-

1214

AN NMR STUDY

Vol. 9, No. U

TABLE I Coupling

i,,

Constants

JII7snCCH

Compound

of P h e n y l t i n

JII9snCCH

JII7snCCCH

Trihalldes a JI19snCCCH

Jom

J

|

C6HsSnCI 3

op

b

118

124

53

61

8.3

1.5

C6HsSnBr 3

Ii0

121

50

59

8.3

1.5

C6HsSnI3 c

105

111

~ In

Hertz on neat liquids

J119SnCCCC H ~33Hz Csatellites not well resolved

ments

(8).

However,

ortho

proton

polar

and

term

is

has

proximity

in

addition

to

is

such

so

a mixture

the

that

Fermi

that JSnCCH

of JSnCCH"

is much larger

of

di-

Similar and in

than JSnCH

than the latter by complex

formation

(ca. 200 Hz) in the ethyl-

trlhalldes.

Since the Fermi

in the phenyl derivatives,

which results

the

contact

in the ethyltln halides

of the coupling must reflect

in the ethyl d e r i v a t i v e s

the lower

the inSnCC angle

in a shorter distance between

and tin atoms.

The value of J

om

in substituted

to the e l e c t r o n e g a t l v i t y in electron w i t h d r a w i n g

(6, i0).

is related The v a r i a t i o n

power of the tin atom on going from phenyl-

to the tribromide

change

The value obtained

.

benzene molecules

of the substltuents

tin trlchloride

is not sufficient for J

om

is larger

atom

the m a g n i t u d e

than in the phenyltin

creased magnitude

in J

tin

of JSnCCH are much larger

term should be larger

the hydrogen

system

the

is less perturbed

The values

the

to

prevail

it is observed

tin trlhalides

of

in d e t e r m i n i n g

considerations

and the former

contact

geometry

contributions

important

these systems

(9).

some

orbital

geometrical

the

than a previous

for phenyltln om

estimate

(ii).

to cause any trlchloride

Vol. 9, No. 11

~

Investigations in the p r e s e n c e the Lewis

acid

Therefore,

behavior

(X - CI,

Br)

be found

in Table

1215

of the b e h a v i o r

of Lewis

we have

N-MR STUDY

bases

has been

of m e t h y l t l n

investigated

in the p r e s e n c e If.

of J S n C H

of v a l u e

halides

of v a r i o u s

TABLE

Lewis

in u n d e r s t a n d i n g

of J S n C C H bases.

in o b s e r v i n g

(12,

13).

for C 6 H s S n X 3

The data m a y

satellites

in any-

II

with Added

of Jl19

halides

in s o l u t i o n

the v a r i a t i o n

The d i f f i c u l t y

Variation

of m e t h y l t l n

Lewis

Base

SnCCH Lewis

Base

C6H5SnCl 3

Carbon tetrachlorlde D i e t h y l ether D i b u t y l ether Dibutyl sulfide Tetrahydrofuran Tetrahydrothlophene Benzyl a l c o h o l Benzyl thlol Acetone Methanol

thing but between such

the o b s e r v e d

and d i p o l a r

in a smaller

trends

fide and

the donor

tetrahydrothlophene)

oxygen Thus, tion

acid,

coordination it appears

in tin

the base

and

(IV)

oxygen

there

the tin atom.

that

sulfur

base.

base

between

constant

formation. there i.e.

However,

alcohols

effects tin

should

is an i n c r e a s e > ketones

(dibutyl a larger

(IV)

of p r e f e r e n t l a l of

in s o l u t i o n

The c o m p l i c a t i o n

in two cases

Although

adducts

the b a l a n c e

complexes

bases,

of the base

is a r e p o r t

in thloxan

that

the

(13).

on adduct

to note

correlation

of the a d d u c t s

to the c o u p l i n g

For o x y g e n ability

any direct

chloride

change

It is of i n t e r e s t

to be a hard

and AHf

contributions

overall

than the c o r r e s p o n d i n g

121 121 121 123 130 131 124 121 127 139

precludes

trimethyltln

can be noted.

in J S n C C H with > ethers.

solutions

variations

as is found w i t h

result some

124 125 124 128 124 131 134 124 127 128

concentrated

of o r b i t a l

C6H5SnBr 3

sulchange

is c o n s i d e r e d

sulfur

over

tin t e t r a h a l l d e s

(14).

oxygen

coordina-

may be d e t e r m i n e d

or sulfur

by groups

attached

to

1216

AN NMRSTUDY

Vol. 9. No. 11

It is clear from this study that satellite spectra analysis in aryltin alkyltln

(IV) compounds is not as useful a technique as it is in

(IV) species.

However, with the use of time averaged or

Fourier transform nmr spectroscopy some of the difficulties inherent in the present study could be avoided.

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