ACETYLENE INSERTION AND DOUBLE INSERTION REACTIONS OF RHODIUM HYDRIDO COMPLEXES

RhH(L)(PPh33 (L = CO or PF3) react with RCCR (R = CF3, or CO2Me) to give vinyl complexes trans-RH(L)(PPh3)2(CRCHR). These complexes undergo further acetylene insertion; e.g., trans Rh(L)(pph3)2(CR1CHR1) (R1 CF3) reacts with R2CCR2 (R2 = CO2Me) and transRh(L)(PPh3)2(CR2chr2) reacts wutg R1CCR1 to give unexpectedly the same double inserted product transRh(L)(PPh3(PPh3)2(CR2CR1CHR1) and a possible reaction mechanism is presented. Rh(PF3)(PPh3)2 [C(CF3)CHCF3] and tbutyl bromide give CF3CHCHCF3,isobutene and transRhBr(PPh3)2(PF3). © 1979.