React ion of ([I) with HC1. To a solution of 0.34 g (0.50 mmole) of complex ([I) was added excess HC1 in dioxane at 20 ~ The co lor of the solution changed to g r e e n and a p rec ip i t a te deposited. The prec ip i ta te was separa ted by f rac t iona l c rys ta l l i za t ion f r o m toluene into CP2VC12 (0.09 g; 0.38 mmole) and CdC12 (0.06 g; 0.35 mmole) . Analys i s by GLC disc losed that the reac t ion mix tu re contained 0.032 g (0.20 mmole) of Et3GeH and 0.098 g (0.50 mmole ) of EtsGeC1.

T h e r m a l Decomposi t ion of (II). A solution of 0.39 g (0.58 mmole) of complex (II) in 10 ml of toluene was heated at 100 ~ fo r 2 h. Here 0.045 g (0.40 mmole) of Cd deposi ted. Analys is by GLC disc losed that the reac t ion mix tu r e contained 0.044 g (0.28 mmole ) of Et3GeH and 0.098 (0.50 mmole) of Et~GeC1. Frac t iona l subl imat ion of the solid res idue in vacuo gave 0.028 g (0.32 mmole) of Cp2V and 0.70 g (0.14 mmole) of Cp2VC1.

CONCLUSIONS

1. Using an equ imolar ra t io of the r eac tan t s , the reac t ion of bis (cyclopentadienyl)vanadium dichloride with bis ( t r i e thy lgermyl )cadmium gave a complex of compos i t ion [Cp~VC12 �9 Cd(GeEt3)2].

2. The complex when heated or r eac ted with HC1 decomposes with the l ibera t ion of cadmium (o rcadm[um chloride) and c leavage of the V--Ge bond.

1.

2.

L I T E R A T U R E C I T E D

G. A. Razuvaev, V. N. La tyaeva , L. I . Vyshinskaya (L. J . Vishinskaya) , V. T. Bychkov (By~hkov) , and G. A. Vas i lyeva , J . Organomet . Chem. , 87_, 93 (1975). V. T. Bychkov, I. V. Lomakova, and G. A. Domrachev , Izv. Akad. Nauk SSSR, Ser. Khim., 1975, 2115.

D I P O L E M O M E N T S O F S O M E

R. R. S h a g i d u l l i n , I. I. a n d I . A . N u r e t d i n o v

SE L E N O P H O S P H O R Y L C O M P O U N D S

V a n d y u k o v a , UDC 541.67 : 547.1'118 : 546~

The data on the dipole momen t s (DM)ofse lenophosphoryl compounds (SPC) a r e ve ry scanty [1-3]. The p r e sen t p a p e r is devoted to a sys t ema t i c study of the DM of this s e r i e s of compounds.

As can be seen f rom Table 1, the po la r i ty of the studied compounds is quite dependent on the nature of the subst i tuents at the P a tom. Fo r example , it might be ment ioned that when going f rom the dichlor ides of selenophosphonic acids (I)- (III) to the chlor ides of selenophosphinic acids (IV)- (VI) the DM inc rea se s by approx- imate ly 1 D. The value of the DM is p rac t i ca l ly constant in the s e r i e s of phosphorus-conta in ing seleno acid d imethy lamides . E s t e r s (XVII)-{XXVI) a r e m o r e sens i t ive to the nature of the subst i tuents at the P a tom. The DM of these compounds va ry in the l imi t s 2.75-6.65 D, which can be explained by the nonuniformity in the con- fo rma t ion of the (X-VlI)-(XXV) molecu les [2].

In many r e s p e c t s the p r o p e r t i e s of the molecules of SPC a r e de te rmined by the P = Se grouping. In this connect ion the value of p P=Se and its dependence on the nature of the subst i tuents at the P a tom s e e m s of in- t e r e s t . A method that is extensively used to de te rmine p P=X wheu studying the DM of organophosphorus c o m - pounds is that of vec to r subt rac t ion: ~ p=X=~R1 2 -P=X - - ~ R 1 2 -i~ [4-7]. The absence of s t ruc tu re data, the

�9 t ~. j ~ poss ib i l i ty of conformat iona l equi l ibr ium, anda l so the depend~nce of the DM of the bonds on the c h a r a c t e r of the envi ronment [4, 6, 7], a l l r e s t r i c t the use of the vec to r addit ive scheme in genera l and the above given equation in pa r t i cu l a r . Taking all of the above into account, fa i r ly c o r r e c t values of # P=Se can be obtained in the studied s e r i e s of SPC (see Table 1) only for the s y m m e t r i c a l l y subst i tuted compounds (X}, (XI}, and (XXVI). It is in te res t ing to c o m p a r e the #P=X for X=O, S, Se, which was done by us in Table 2 on the bas i s of the obtained and l i t e r a tu re data. A s can be seen f rom Table 2, for the t r i s (dimethylamino} and tr iphenyI de r iva t ives the value of the DM of the molecu le and the P = X bond inc rea se in the o rde r : X=Se > S �9 O. How- ever , the opposite o rde r is observed for the bicycl ic e s t e r s of phosphorus acids and MeP(X)C12. As a resul t , the re la t ive po la r i ty of the P =X bond (and the molecule) in oxides, sulf ides, and se lenides can be r eve r sed

A. E. Arbuzov Insti tute of Organic and Physica l Chemis t ry , Kazan Branch of the Academy of Sciences of the USSR. Trans l a t ed f r o m Izves t iya Akademit Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1407-1409, June, 1978. Original a r t i c l e submit ted July 14, 1977.

0568-5230/78/2706-1225 $07.50 �9 1978 Plenum Publishing Corpora t ion 1225

TABLE I , CC14)

Com - pound

(I) (II)

(III) (IV) (V)

(VI) (VII)

(VIII) (IX) (X)

(XI) (XlI)

(XlII)

Dipole Moments of Selenophosphorus Compounds (in

Formula

MeP (Se) C12 EtP (Se) CI~ PhP (Se) C12 Et~P(Se)C1

Ph2P (Se) C1 Bu2P (Se) H Ph2P (Se) H Et3P (Se) Ph3P (Se) P (Se) (NMe2) s MeP (Se) (NMe2) EtP (Se) (NMe2)

* In d ioxane .

~, D Compound

2,89 (XIV) 3,07 (XV) 3,67 (XVI) 4'22 (XVII) 4,37 (XVIII) 4,5t (XIX) 4'49 (XX) 4'29 (XXI) 5,i2 (XXII) 5,06 (XXIII) 5,12 (XXIV) 4,91 (XXV) 4,89 (xxvI)

Formula

PhP (Se) (NMe2) z Et~.P (Se) NMe2 Ph~P (Se) NMe2 (MeO) sP (Se) (EtO) sP (Se) (/-PRO) sP (Se) (PRO) sP (Se) (BuO) sP (Se) (i-BuO) ~P(Se) (MeO) 2P (Se) Me MeOP (Se) Et2 MeOP (Se) Ph2 MeC (CH~O) ~P (Se)

~,D

4,83 4,77 4,71 2,75 2,80 2'70 [21 3,05 3,O5 2,95 2,97 3,90 [31 3,9o 6,65 *

TABLE 2. D ipo le M ome n t s of Y3 p =X M o l e - c u l e s and P = X bonds (in p a r e n t h e s e s )

Y s

Phs,

CHaC (CH~O) 3

(Me2N) 3

MeClz

PhzNMe2

O �9

~5i i l l (3,27)

7,i0 [5] (2,95)

4'3! [6] (3,07)

3,35 [4] (3,t3)

4,29 [61

X

4'88 [1] (3,55)

6,77 [5] (2,62)

4,49 [6] (3,25)

3,00 [4] (2,63)

4,37 [6]

Se

5,17 [l] (3,73) 6,65

(2,5O) 5,12

(3,88) 2,S9

~7i

/~, D

#

y

!

2

o,2 0,6 ~o ~,~ ~e ~ o i

F ig . 1. R e l a t i o n b e t w e e n ~ P=X and ~ i f o r s o m e s y m m e t - r i c a l l y s u b s t i t u t e d Y3P- -X c o m p o u n d s : 1) g r a p t ~ . c a l a v e r - ag ing of da t a g i v e n in [1] f o r PffiO, l~p=o=-O.3Zai +3.2 ( r= - 0 . 7 9 ) ; 2) f o r P = S [1], # p = s = - l . 4 Za i +3.8 ( r f f i -0 .99 ) ; 3) f o r P = S e .

depend ing on the c h a r a c t e r of the s u b s t i t u e n t s . H e r e the v a r i a b i l i t y is # p=O < # P=S (in h a r m o n y wi th [1, 4, 7]) </~ PffiSe" In h a r m o n y wi th [1] and the r e s u l t s of o t h e r s t u d i e s i t m a y be conc luded tha t both the p o l a r i z a b i l i t y and doub le bond c h a r a c t e r of t he P f X g r o u p i n g d e c r e a s e s in t he s a m e o r d e r .

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It might also be mentioned that a qualitative relationship exists between the electron-donor [11] andpolar properties, expressed by the DM of SPC molecules. Attempts to compare the DM of the phosphoryl group and its ability for H bonding are known [12]. The corresponding correlations in the series P=X (X=O, S, Se) aiso represent interest, but require a larger number of fairly correct # P=X values.

EX PE RIME NTAL

The dipole moments were measured as described in [2, 3]. The compounds were obtained as described in [13, 14]. The structure and purity of the compounds were confirmed by the elemental analysis, IR, arid NMR spectral data.

The authors express their gratitude to D. N. Sadkova for assistance in the experimental work.

CONCLUSIONS

I. The molecular dipole moments (DM) of the 26 studied selenophosphoryl compounds vary in the range 2,70-6.65 D. The reasons for the changes in the DM are discussed.

2. The dipole moments of the P=Se bond displays a greater variability than do P =S and P=O. Accord- ing to the obtained and literature data, the polarizability and coordination character of the P=X bond changes inthe order: P=Se>P=Se>P=O.

L I T E R A T U R E C I T E D

1. R .R. Carlson and D. W. Week, Inorg. Chem., 13, 1741 (1974b 2. R .R . Shagidullin, I. I. Vandyukova, I. A. Nuretdinov, and Kh. Kh. Davletshina, Dold. Akad. Nauk SSSR,

225, 886 (1975). 3. I . I . Vandyukova, R. R. Shagidullin, and I. A. Nuretdiuov, Izv. Akad. Nauk SSSR, Ser. Khim., 1976, 1390. 4. B.A. Arbuzov and R. P. Arshinova, Dold. Akad. Nauk SSSR, 22.7, 1361 (1976). 5. A . L . McClellan, Tables of Experimental Dipole Moments, Vol. 2, Rahara Enterprises, E1 Cerrito (1974). 6. E .A. Ishmaeva, M. A. Pudovik, I. Ya. Kuramshin, L. P. Ivantaeva, and A. N. Pudovik, Izv. Akad. Nauk

SSSR, Ser. Khim.9 1977, 178. 7. S . t . Vdovenko, V. Ya. Semenii, Yu. P. Egorov, Yu. Ya. Borovikov, and V. N. Zavatskii, Zh. Obshch.

Khim., 46, 2608 (1976). 8. E . L . Wagner, J. Am. Chem. Soc., 85, 161 (1963). 9. L . C . Thomas, Interpretation of the Infrared Spectra of Organophosphorus Compounds, Heydeu, London

(1974). 10. M. Charton, J. Org. Chem., 29, 1222 (1964). 11. R .R . Shagidullin, I. A. Lipatova, I. A. Nuretdinov, and S. A. Samartseva, Dokl. Akad. Nauk SSSR, 221,

1363 (1973). 12. U. Blindheim and T. Gramstad, Spectrochim. Acta, 21, 1073 (1965). 13. N.P. Grechkiu, I. A. Nuretdinov, N. A. Buina, and L. K. Nikonorova, Chemistry and Application of Or-

ganosphosphorus Compounds, Transactions of Fourth Conference [in Russian], Nauka (1972), p. 350. 14. K. Sasse, Houben-Weyl, Methoden der Organlscheu Chemic, Vol. 12, Stuttgart (1963).

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