The nature of sulphinate coordination in some organothallium sulphinates

1N0R6.

NUCL.

CHEM.

LE77ER5

V01.

6,

pp.

71%721,

1970.

Per9am0n Pre55.

Pr1nted 1n 6 r e a t 8r1ta1n.

7HE NA7URE 0F 7HE 5ULPH1NA7E C00RD1NA710N 1N 50ME 0~6AN07HALL1UM 5ULPH1NA7E5

6.8. Deac0n and V.N. 6ar9 Department 0f Chem15try, M0na5h Un1ver51ty, C1ayt0n, V1ct0r1a, Au5tra11a, 3168. ~e~ed

4 May 1970~

A5 part 0f the current 1ntere5t 1n 5u1ph1nate c0mp1exe5, there have 6een a num6er 0f 1nve5t19at10n5 0f der1vat1ve5 0f a1um1n1um, 9a111um, and 1nd1um (1). 8y c0ntra5t, 0n1y tw0 tha111um(111)

5u1ph1nate c0mp1exe5 have 6een rep0rted, v12.

71C12(025-~-MeC6H 4) (2) and Me271(025Me)

(3).

We have n ~

1nve5t19ated the nature

0f the 5u1ph1nate c00rd1nat10n 1n a num6er 0f c0mp1exe5 0f the type5, R271(025R•) and R2(phen 0r 61py)71(025Rt)

(phen ~ 1,10-phenanthr011ne;

61py = 2,2~-61py-

r1dy1) . 7he c0mp0und5 prepared are 115ted 1n the 7a61e.

Der1vat1ve5 0f the c1a55

R271(025R•) were 06ta1ned 6y react10n 0f 511ver 6en2ene- 02 ~-t01uene-5u1ph1nate (~) w1th the appr0pr1ate d10r9an0tha111um(111) ch10~1de 0r 6r0m1de 1n methan01, wh115t R2(phen 0r 61py)71(025R•)

c0mp1exe5 were prepared 6y react10n 0f e4u1m01ar

am0unt5 0f the d10r9an0tha111um(111) 61pyr1dy1 1n methan01.

5u1ph1nate5 and 1,10-phenanthr011ne 0r 2,2 t-

D1mathy1- and d1ethy1-tha111um(111)

n0t 91ve c0mp1exe5 w1th 2,2~-61pyr1dy1, w1th 1,10-phenanthr011ne. (C6F5)271(025Ph) , F0und:

6en2ene5u1ph1nate5 d1d

and the f0rmer d1d n0t y1e1d a c0mp1ex

A11 pr0duct5 were 06ta1ned ane1yt1ce11y pure, e.9. C, 31.4; H, 1.1; F, 27.6; 5, ~.7; 71, 29.7.

C~8H5F1002571 re4u1re5 C, 31.8; H, 0.7; F, 28.0; 5, 4.7; 71, 30.1%.

5u1phur-

0xy9en 5tretch1n9 fre4uenc1e5 0f the c0mp0und5 are 91ven 1n the 7a61e.

7he

~5519nment5 f0110~ fr0m c0mpar150n 0f the 5pectra 0f the 5u1ph1nate c0mp1exe5 w1th th05e 0f 5u1ta61e reference c0mp0und5 1nc3ud1n9 the appr0pr1ate d10r9an0tha111um(111) ha11de5 (5-~) and (C6F5)2(phen 0r 61py)71(C1 0r 8r) (5, ~). ~7

718

5ULPH~A7E

C00RD1NA710N

V 0 1 . 6 , N0. 8

7A~LE Pr0per~1e5 0f 50me 0r9an0tha111um 5u1ph1nate C0mp1exe5

v(502)

v(502)

5011d 5tate

1n CHC13

C0mp0und

943v5(6r)

Et27~(025Ph)

,,27~{0~5.h~ Ph271(025Ph)

1005v5 (6r) 981ve

1014a

948e(6r) ~

951ve

~

936ve

~

(C6F5)271(025Ph)

884e (6r)

m

6

~%%~ ~71~0.~5-~-~ec#4~

881v5(6r)

~

•

Et2phen71(025Ph)

1031v5(6~)

964v5

10185

Ph2phen71(025Ph)

9565(6r) ,

Ph261py71(025Ph)

(C6F5) 2Phen71(025Ph)

1032m

928v5

(~)261py71(025Ph)

1009v5~d

917m

c~a.1021 5h(6r)

9185(6r)

1014m(6r) ~

919m(6r)

~c~%~~ 0 2 5 - ~ - . e c ~

924m(Y6r) 101101 1} ~(6r)

( C6F5 ) 261p~71( 025-~-N eC6H4)

1013v~dd

ca0925m(v6r)

1014m~d

915m(6r)

P055161y 50me 1nten51ty 0f 5 med1um 6r0ad a650rpt10n at 917 cm -1 5h0u1d a150 6e attr16uted t0 V(502). 6 -

-

1n501u61e. 1n1t1a11y 501u61e, 6ut Ph271(025Ph) 15 rap1d1y prec1p1tated. 0ther 119end m0de5 a150 c0ntr16ute t0 the a650rpt10n.

V~.6,

N~ 8

5ULPH~A7E

~ e ~ t h ~ 1 1 1 e15ct~1~te 5tretch1n9

ethane5u1ph1nate

1n methan01, fre4uenc~e5

5tructure

c0mp1exe5 1.

7~

15 a ~ t ~ 1 y t e

d1mer1u 1n ch10r0f0rm,

1n acet0ne,

(8).

~

a 1:~

end he5 51m11~r 5u1phur-0xy9en

1n the 5011d 5tate an~ ~n ch10r0f0rm

6e1n9 ~1th1n the ran9e f0r ~ ~ h ~ e

C00RD1NA710N

~7a61e), the va1ue5

c0mp1exe5 and ~e11 0ut5~de the ran9e f0r

Acc0rd1n91y,

the c0mp0und

15 c0n51dered t0 have

7he h19h c0nductance 1n methan01 5u99e5t5 that the 6en2ene5u1ph1nate Ph

Ph

9r0up5 are n0t 5tr0n91y 60nded t0 tha111um. t ha111um(111>

c0mp0und5

1 have 6een pr0p05ed 0r 1n) der1vat1ve5

are e1ectr01yte5

f0r Me271(025P~e)

(1).

fre4uenc1ee

5u1ph1nate5

c0mp0un~5 prevent5

fre4uenc1e5

fre4uenc1e5

1n acet0ne

and hence ~hether 0r n0t the C71C 6en2ene- and ~-t01uene-

are 501c1~ attr16uta61e

c0mp0und5

c00rd1nat10n,

c0mp0und5.

1n ch10r0~0rm

1t 15

t0 the d1fferent

d1fference5 are a150 1nd1cated.

are 1n501~61e

1n

c0mp0und5.

(8) 0f ~-5u1ph1nate

fr0m th05e 0f 0ther R271(025R~)

(R) 0r ~hether 5tructura1

0f the

and have m01ar c0nductance5

are 1nd1cat1ve

n0t c1eer ~hether the5e d1fference5

51nce (C6F~)271(025R~)

1n methan01.

determ1nat10n

1e55 than th05e 0f the 0ther R271(025R~)

they a15c d1ffer 5 1 9 n 1 f ~ a n t 1 ¥

0r9an1c 9r0up5

(M = A1, 6a,

6en2eneeu1ph1nate5

and are 1:1 e1ect~01yte5

815(pentaf1u0r0pheny1)tha111u~(1]])

are n0m-e1ectr01~te5

A1th0u9h the V(502)

51m11ar t0

7he c0mp1ex1ty 0f the 5pectra (600-450 cm -1) 0f the

act1ve y(71-C)

methan01 519n1f1cant~y

5tructure5

51m11ar t0 th05e 0f Et271(025Ph) , 5tructure5

d1methy1- and d1ethy1-tha111um(1]])

5ke1et0n 15 11near.

(5).

D•m5thy1- and d1pheny1-tha111um(11~1

51m11ar t0 1 5eem 11ke1y.

num6er 0f 1nfrared

1n methan01

(~) and f0r 5evera1 R2M(025R~)

are 1n 501u61e 1n acet0ne and ch10~0f0rm 51nce they have ~(502)

A num6er 0f 0ther n0n-10n1c d10r9an0-

H0~ever~

[~herea5 ~he c0rre5-

720

5ULPH1NA7E

p0nd1n9 (C6F5)2(phen 0r 61py)71(025R•)

C00RD~A~0N

V01. 6, N0. 8

c0mp1exe5 are 501u61e] and 0n1y 5par1n91y

501u61e 1n acet0ne, they appear t0 have 50me 50rt 0f a550c1ated 5tructure, pre5uma61y 1nv01v1n9 6r1d91n9 ~-5u1ph1nate 9r0up5. 7he c0mp1exe5 (C6F5)2(phen 0r 61py)71(025R•) Et2phen71(025Ph)

(R• = Ph 0r ~-MeC6H 4) and

are n0n-e1ectr01yte5 1n acet0ne, m0n0mer1c 1n ch10r0f0rm, and

have 51m11ar V(502) fre4uenc1e5 1n the 5011d 5tate and 1n ch10r0f0rm, the va1ue5 1nd1cat1n9 ~-5u1ph1nate c00rd1nat10n.

7hu5, the c0mp1exe5 have m0n0mer1c 5truc-

ture5 w1th e1ther f1ve c00rd1nate tha1J~um and un1d~ntate ~-5u1ph1nate 9r0up5 0r 51x c00rd1nate tha111um and 61dentate ~-5u1ph1nate 9r0up5.

7he f0rmer arran9e-

ment 15 preferred, 51nce f1ve c00rd1nat10n 15 c0mm0n (5,9) an0 m0n0mer1c 51x c00rd1nate 5tructure5 are rare (10) am0n95t 1501a61e c0mp1exe5 0f d10r9an0tha113um(111) c0mp0und5.

7he Ph2(phen 0r 61py)71(025Ph) c0mp1exe5 pr06a61y have

51m11ar 5tructure5 6ut pr0pert1e5 0f the c0mp0und5 1n ch10r0f0rm c0u1d n0t 6e 5tud1ed a5 the 501ut10n5 rap1d1~ dep051t Ph271(025Ph). At f1r5t 519ht the pmeference 0f tha111um f0r ~-5u3ph1nete c00rd1nat10n 5eem5 5urpr151n9 51nce 713+ (and Me371) are 50ft ac1d5 (11), wh1ch 1n 9enera1 91ve A-5u1ph1nat e c0mp1exe5.

H0~ever, there 15 ev1dence (5) that (C6F5)271+

can 6ehave a5 e1ther a hard 0r a 50ft ac1d, and at 3ea5t 0ne 50ft ac1d, Cd 2+ (11), 91ve5 ~-5u1ph~nate c0mp1exe5 ~12).

7h15 5tudy 15 current1y 6e1n9 extended

t0 a w1der ran9e 0f 0r9an0tha11~um 5u1ph1nate c0mp1exe5.

Ackn0~v1ed9ement:

We are 9ratefu1 t0 the Au5tra11an Re5earch 6rant5 C0mm1ttee f0r

5upp0rt.

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5ULPH1NA7E C00RD1NA710N

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