Synthesis of 3-stannyl and 3-silyl propargyl phosphanes and the formation of a phosphinoallene

摘要

The group 14 chloropropargyls R3EC CCH2Cl (R3E = (Bu3Sn)-Bu-n, Ph3Sn, Me2PhSi, (Pr3Si)-Pr-i, (Pr3Si)-Pr-n, (Bu3Si)-Bu-n), obtained by a modified literature procedure, react with LiPPh2 to afford the novel propargyl phosphanes Ph2PCH2CuCER3 in high yield, as viscous oils; (Me3Si)(2)PCH2C CSiPhMe2 is similarly obtained from LiP-(SiMe3)(2). In contrast, the reaction of PhC CCH2MgCl with ClP(NEt2)(2) fails to produce a comparable propargyl phosphane, but generates preferentially (>70%) the novel phosphinoallene (Et2N)(2)PC(Ph)=C=CH2, which is characterised spectroscopically, and through its reaction with HCl. The coordination chemistry of representative phosphanes is explored with respect to platinum and palladium for the first time.