Trimetallic ReBiPt complexes containing spiro-bismuth ligands from the reaction of the bis(tri-t-butylphosphine) platinum with Re3(CO)12(μ-BiPh2)(μ-H)2

Pt(P-t-Bu-3)(2) reacts with the bismuthtrirhenium complex Re-3(CO)(12)(mu-BiPh2)(mu-H)(2), 1 at 68 degrees C to give eight complexes PtRe2(CO)(9)P(t-Bu-3)(mu-H)(2), 2, PtRe3(CO)(12)P(t-Bu-3)(mu-Ph)(mu-H)(mu(4)-Bi), 3, PtRe3(CO)(13)P (t-Bu-3)(mu(4)-Bi)(mu-H)(2), 4, PtRe4(CO)(16)P(t-Bu-3)(mu-H)(2)(mu(4)-Bi)(m(3)-Bi), 5, Pt2Re5(CO)(21)[P(t-Bu)(3)](2)(mu-H)(3)(mu(4)-Bi)(2), 6, trans-Pt2Re5(CO)(22)[P(t-Bu)3](2)(mu-H)(3)(mu(4)-Bi)(2), trans-7, cis-Pt2Re5(CO)(22)[P(t-Bu)(3)](2)(mu-H)(3)(mu(4)-Bi)(2), cis-7, (an isomer of trans-7) and Re-3(CO)(13)[PtPBu3t]2(mu-H)(2)(mu(4)-Bi), 8, all in low yields. When 4 was treated with Pt(P-t-Bu-3)(2) at 68 degrees C, compounds 2, trans-7, cis-7, and Pt2Re4(CO)(18)[P(t-Bu)3]2(mu-H)(2)(mu(4)-Bi)(2), 9 were formed. When 8 was treated with CO at 25 degrees C, compounds 2, trans-7, 9, and PtRe3(CO)(9)P(t-Bu)(3)(mu(3)-Bi) (mu(4)-Bi-2), 10 were formed. In all of the products both of the phenyl rings from the bridging BiPh2 ligand of 1 were cleaved from the bismuth atom. Only compound 3 contains a phenyl ligand and that ligand was a bridging ligand across the Pt-Re bond. All of the products, except 10, and the known compound 2, contain spiro, mu(4)-Bi ligands. The higher nuclearity complexes 5, 6, trans-7, cis-7, and 9 contain two bismuth ligands. Compound 10 contains three bismuth atoms. Two of the bismuth atoms in 10 are part of an octahedrally-shaped Re3PtBi2 cluster. The third bismuth atom is a triply-bridging ligand on the triangular Re3 face of the cluster. When a mixture of 4 and 8 was heated to 68 degrees C in the presence of CO, the new compound PtRe4(CO)(17)(P-t-Bu-3)(mu-H)(2)(mu 4-Bi), 11 was formed. The molecular structures of all of the new complexes were characterized by single-crystal X-ray diffraction analyses. (C) 2010 Elsevier B.V. All rights reserved.