Selective substitution and oxidative addition reactions at the iridium vertex in [Re 7C(CO) 21Ir(C 8H 14)(CO)] 2− and related clusters

Abstract

The heterobimetallic cluster complex [Re 7C(CO) 21Ir(C 8H 14)(CO)] 2− undergoes a variety of reactions (e.g. with carbon monoxide, phosphines, phenylacetylene, hydrosilanes and alkyl halides) selectively at the iridium vertex to give substitution and oxidative addition products. [PPN] + and/or [Et 4N] + salts of several cluster derivatives, such as [Re 7C(CO) 21Ir(L)(CO)] 2− (L=CO, PMePh 2 and PPh 3), [Re 7C(CO) 21Ir(H)(SiPh 3)(CO)] 2− and [Re 7C(CO) 21Ir(η 3C 3H 5)(CO)] −have been isolated and fully characterized by analytical and spectroscopic data. [Re 7C(CO) 21Ir(CO) 2] 2− and [Re 7C(CO) 21Ir(H)(SiPh 3)(CO)] 2− also react selectively with tertiary phosphines to afford the PMePh 2 and PPh 3 derivatives [Re 7C(CO) 21Ir(CO)(PR 3)] 2−, respectively.