Microscopía electrónica de transmisión (MET)

formation appear to be very long. Thus the complicated init-

4 iation process may be capable of representation by equation (1),

Me GeOl* + Me,GeH j. Me-GeOlH + Me,Ge’ (3) |

tS-

■Me_Go* -+ M e ^ G e * ^ Me^Ge. -(h) '4

3 3 D 2 •

(where 01 represents olefin).

?

In preliminary experiments with each of the unsymm- etrical fluoro-ethylenes, it was found that the adduct ratios did not appear to change uniformly with temperature as was the case in the addition of n-heptafluoropropyl, methyl and ethyl radicals. Also,, the amount of the termination product, hexamethyldigermanium, increased with increasing temperature. This could be explained in three ways, (a) the recombination of trimethylgermyl radicals had an activation energy, (b) the

%

-reaction (2) was reversible or (c) in the initiation, f I was, il

' ^ #

in some way, temperature dependents The -fir-st -explanation seemed unlikely in view of the fact that trimethylsilyl rad-

109 icals are known to recombine without an activation energy. ^ In view of the fact that the chains were very long, explanation

This left (b) as the most likely explanation for the observed effects.

If reaction (2) is considered to be an equilibrium and reaction 11) is a valid representation of the Initiation process, then application of steady state theory to the prop­ osed mechanism gives:

dlMegGe^]

= ^ 1 / 4 (A)

dt

dlMo^GeOlH] k^kg(/iy4k^l'atoll [Me GeH]

•(B) and

dt Me^GeH]

(Me,Ge ] k, \

--- — T = _ 4 ._ oT U ^ 1- /kJMe GeH]

GsOIHI - Ms_6eHl ?lc. Oil . \ " ^ ^ 4

1 He^GeOlH] Mo GeH] 2k^ [Ol] ^

(C)

108.

?

From equation (C), a plot of [l^Ie^GeH]^

against l/[Me Geflj should be a straight line with gradient

(the derivation of these equations is shown in appendix III)

Equation (A) implies that the concentration of hexa- | methyldigeriaanium should be linearly related to light intensity.

This was found to be the case (table III~6) and so reaction (1) g

appears to be a reasonable approximation. From the slope of the plot of [Me^Ge’^]/[Me^GeHj against I^, a value of 2.616 x 10"^ mole l"^ quantum"^ was obtained for ^ for the initiation.

-Actinometry using potassium ferrioxalate gave the light intensity

% 4L

and intercept Ck^^Vk^ vfhere C s [Ol] ^

when experiments are carried out at constant temperature and initial olefin concentration. (The value of 0 for the experiments of table 1II-3 is 3*71 x 10^,) Such experiments were carried out

in which the olefin was 1 ,1-difluoro-ethylene (table I I I - 3 )

and straight line plots were obtained (figure III-2). If it is

assumed that C is temperature independent, that is, that is

not temperature dependent, then, with a knowledge of the rate constant for the recombination of trimethylgermyl radicals, estimates can be made ©Ç the Arrhenius parameters for the addi­ tion reaction and of-the-ratio, k_^/k^.

Although the recombination and cross combination rate constants have been determined for many carbon radicals, there are few such studies for radicals of the other group IVb elements. The only radicals studied in the gas phase have been those of silicon. Recently, Watts and Ingold measured the recombination rate constants for a variety of group IVb radicals in solution using electron paramagnetic r e s o n a n c e . T h e y found that the rate c o n s t a n t s d e cre a s e d a s t h e m o l e c u l a r v /ei g h t o f t h e r a d i c a l i n c r e a s e d , a n d t h a t a g o o d c o r r e l a t i o n w a s o b t a i n e d b e t w e e n

-log 2k^ and molecular weight. A similar effect was found by Bertrand et.al for the combination of alkyl and halogenated

111

a l k y l r a d i c a l s i n t h e g a s p h a s e . F i g u r e I I I - 3 s h o w s t h e c o r r e l a t i o n s f o u n d b y b o t h s e t s o f w o r k e r s . F r o m t h i s f i g u r e , a n e s t i m a t e f o r t h e r e c o m b i n a t i o n r a t e c o n s t a n t o f t r i m e t h y l - g e r m y l r a d i c a l s i n t h e g a s p h a s e v / o u l d b e 1 0 ^ ' 1 m o l e ” ^ s " ^

110.

Figure III-2a Plot of Equation (A) for Addition of Me^GreH to in

^1o 1 y1-Difluoroethylene at 68° and 98^. jH

8

0

7.0 ■

3.0

2

0

5.0

6.0

7.0

6.0

9.0

l/[MeoGeH]i

10 1/

1,1-Pifluoroethylene at

119

8

8.0

7-0 •

2

0

1

0

AT =115'

@T = 136'

6.0

8.0

112,

Figure III-5 Correlation of logarithm of rate constants for recombination

of group IVb radicals in the liquid phase v/ith molecular weights.

gas phase data