VINYLIDENE TRANSITION-METAL COMPLEXES .36. OLEFIN, ALKYNE, VINYLIDENE, CARBOXYLATE AND HYDRIDO COMPLEXES CONTAINING [RH(P(T)BU(2)ME)(2)] AS A MOLECULAR UNIT

摘要

The reaction of [RhCl(C2H4)(2)](2) (1) with P(t)Bu(2)Me yields the square-planar complex trans-[RhCl(C2H4)(P(t)Bu(2)Me)(2)] (2) which upon treatment with H-2 gives the dihydride [RhH2Cl(P(t)Bu(2)Me)(2)] (3) and ethane. The alkynerbodium(I) compounds trans-[RhCl(HC=CR)(P(t)Bu(2)Me)(2)] (4-6) which have been prepared from 3 and HC=CR (R = H, Me, Ph), thermally rearrange to the isomeric vinylidene derivatives trans-[RhCl(=C=CHR)(P(t)Bu(2)Me)(2)] (7-9). The synthesis of the pi-allyl complexes [Rh(eta(3)-2-RC(3)H(4))(P(t)Bu(2)Me)(2)] (11, 12) has been achieved by the stepwise reaction of 1 or [RhCl(C8H14)(2)](2) (10) with 2-RC(3)H(4)MgX and the phosphine. From 11 or 12 and acetic or trifluoracetic acid the monomeric carboxylate compounds [Rh(eta(2)-O(2)CR)(P(t)Bu(2)Me)(2)] (13, 14) have been obtained. Further reaction of 13 and 14 with CO gives the carbonyl derivatives trans-[Rh(eta(1)-O(2)CR)(CO)(P(t)Bu(2)Me)(2)] (16, 17) while on treatment of 14 with ethylene at -20 degrees C the corresponding 1:1 adduct trans-[Rh(eta(1)-O2CCF3)(C2H4)(P(t)Bu(2)Me)(2)] (18) is formed. Both 13 and 14 react with H-2 to yield the dihydrido complexes [RhH2(eta(2)-O(2)CR)(P(t)Bu(2)Me)(2)] (19, 20) and with O-2 to afford the dioxygen adducts [Rh(eta(2)-O-2)(eta(2)-O(2)CR)(P(t)Bu(2)Me)(2)] (21, 22). The O-2 ligand in 21 and 22 is rather weakly coordinated and can be easily displaced by H-2 to give 19 and 20, respectively. [References: 53]