Kuzhikalail M. Abraham

Reactions of oxyl groups on the trimethylsilyl moiety with diphenyl- or dicyclohexyl-chlorophosphines

Treatment of either (C6H5)2PCl with (CH3)3SiOCH3, or (C6H5)2POCH3 with (CH3)3SiCl results in the formation of (C6H5)2PP(O)(C6H5)2. On the other hand, reaction of (C6H11)2PCl with (CH3)3SiOCH3 produces (C6H11)2P(O)CH3. When (C6H5)2PCl is allowed to react with (CH3)3SiOSi(CH3)3, (C6H5)2PP(O)(C6H5)2 and (C6H5)2PP(C6H5)2 are produced. But (C6H11)2PCl shows little reaction with (CH3)3SiOSi(CH3)3 even after heating for five days at ca. 150°.

The reduction of dichlorophenyl- and Chlorodiphenyl-arsines with dimethoxymethylphosphine to form an AsAs bond

Abstract Treatment of 1 mol of C 6 H 5 AsCl 2 with 2 mol or an excess of CH 3 P(OCH 3 ) 2 at room temperature produces C 6 H 5 As[P(O)(CH 3 )(OCH 3 )] 2 . NMR spectroscopic evidence suggests that this compound exists in three diastereoisomeric forms. when an excess of C 6 H 5 AsCl 2 is treated with CH 3 P(OCH 3 ) 2 or when C 6 H 5 As[P(O)(CH 3 (OCH 3 )] 2 is treated with C 6 H 5 AsCl 2 , (C 6 H 5 AS 5 ) 6 is produced. Similarly (C 6 H 5 ) 2 AsAs(C 6 H 5 ) 2 is obtained from either 2 mol of (C 6 H 5 ) 2 AsC1 and 1 mol of CH 3 P(OCH 3 ) 2 or by the reaction of (C 6 H 5 ) 2 AsCl with (C 6 H 5 ) 2 AsP(O)(CH 3 )OCH 3 . Under the experimental conditions employed in this study P(OCH 3 ) 3 failed to reduce either C 6 H 5 AsCl 2 or (C 6 H 5 ) 2 AsCl to yield Asz.sbnd;As bonded compounds.

Exchange and condensation of chloro and methoxyl groups between monomethylphosphino and methyl-substituted silyl or germyl moieties

Abstract The room-temperature reaction between CH 3 PCl 2 and (CH 3 ) x M (OCH 3 ) 4−x , where M = Si with x = 2 or 3, or M = Ge with x = 2, exhibits rapid exchange of chloro methoxyl groups between the starting compounds followed by condensation of the phosphorus moieties to give CH 3 (O)P units connected by PP bonds in the resulting oligomers. When CH 3 P(OCH 3 ) 2 is reacted with (CH 3 ) xitx SiCl 4− x for x = 2 or 3, there is no rapid exchange of chloro and methoxyl groups between the reagents but instead the major observed reaction is a slower condensation of the phosphorus moieties, a process which is necessarily accompanied by a transfer of methoxyl groups from the phosphino to the silyl moiety. In the case of CH 3 P(OCH 3 ) 2 plus (CH 3 ) 2 GeCl 2 , there is essentially no reaction in 2 weeks at room temperature except for a slow rearrangement of the phosphorus compound to (CH 3 ) 2 P(O)OCH 3 .