New High-Nuclearity Carbonyl and Carbonyl-Substituted Rhodium Clusters and Their Relationships with Polyicosahedral Carbonyl-Substituted Palladium- and Gold-Thiolates

Abstract

A reinvestigation of the synthesis of [H(5-n)Rh(13)(CO)(24)](n-) (n = 2, 3) led to isolation of a series of Rh(19), Rh(26), and Rh(33) high-nuclearity carbonyl and carbonyl-substituted rhodium clusters. The [Rh(19)(CO)(31)](5-) (1) is electronically equivalent with [Pt(19)(CO)(22)](4-), but poor crystal diffraction data of all salts obtained to date have prevented its geometrical analysis. The structures of Rh(26)(CO)(29)(CH(3)CN)(11) (2) as 2·2CH(3)CN and [Rh(33)(CO)(47)](5-) (3) as [NEt(4)](5)[3]·Me(2)CO were determined from complete X-ray diffraction determinations. The latter two species adopt polyicosahedral metal frameworks, and notably, [Rh(33)(CO)(47)](5-) represents the molecular group 9 metal carbonyl cluster of highest nuclearity so far reported.