Abstract
1H nuclear-magnetic-resonance was used to investigate exchange of chlorine atoms with methoxyl and dimethylamino groups in the following systems: (1) CH 3Si(OCH 3) 3 vs. CH 3SiCl 3; (2) CH 3Si[N(CH 3) 2] 3 vs. CH 3SiCl 3; (3) (CH 3) 2Si(OCH 3) 2 vs. (CH 3) 2SiCl 2; and (4) (CH 3) 2Si[N(CH 3) 2] 2 vs. (CH 3) 2SiCl 2. Kinetic and calorimetric data were obtained on the two systems (2) and (4) involving exchange of dimethylamino groups with chlorine atoms. In accord with our previous findings on silicon atoms not directly substituted by methyl groups and on triply connected phosphorus atoms, the reorganization equilibria in these four systems were found to be highly nonrandom, with the mixed species being preferred. On the other hand, the equilibria were quite random in the systems: (5) CH 3Si(OCH 3) 3 vs. CH 3Si[N(CH 3) 2] 3 and (6) (CH 3) 2Si(OCH 3) 2 vs. (CH 3) 2Si[N(CH 3) 2] 2. Gas chromatography was used to investigate the nearly ideally random ester-interchange in the systems (7) CH 3Si(OCH 3) 3 vs. CH 3Si(OC 2H 5) 3 and (8). (CH 3) 2Si(OCH 3) 2 vs. (CH 3) 2Si(OC 2H 5) 2.
Published Version
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