2011 年 69 巻 10 号 p. 1099-1108
Polyhedral metal-main group clusters have attracted much attention, because of their structures and properties such as electron transfer and emission as well as a catalyst in organic syntheses. In this paper, we wish to report our recent results concerning the polyhedral platinum-silyl clusters. The reactions of zero-valent platinum complex bearing phosphine ligands with disilanes afforded the trigonal bipyramidal Pt3Si2 or octahedral Pt4Si2 clusters. Use of a sterically small disilane reduces the repulsion between the disilane and the phosphine ligand to induce the formation of higher dimensionally clusters. Each of the platinum-silyl clusters has a polyhedral skeletal structure compressed to Si-Si alignment with long Pt-Pt and short Si-Si distances, compared with those of the platinum clusters including other main group elements such as S, Se, and Ga. The liberation and rebinding of the phosphine ligand regulate a 1,2-migration on the platinum center in the formation process of clusters.