Eleven- and twelve-vertex polyhedral metalladithiaborane chemistry. Novel compounds from the arachno-[S2B9H10]– anion: [(PPh3)3H2IrS2B9H10], [(PPh3)2HIrS2B9H9] and [(PPh3)2HRhS2B8H8]

Abstract

Reaction of the arachno-[S₂B₉H₁₀]^– anion with [IrCl(PPh₃)₃] yields (a)[(PPh₃)₃H₂IrS₂B₉H₁₀], in which cluster–metal interaction occurs solely via heteroatom η¹ two-electron, two-centre, cluster-to-metal donation, and (b)[(PPh₃)₂HlrS₂B₉H₉], which has a contiguous nido-type twelve-vertex cluster structure with η⁵ cluster-to-metal donation, whereas reaction with [RhCl(PPh₃)₃] results in one-atom cluster dismantlings to give nido-type eleven-vertex (c)[(PPh₃)₂HRhS₂B₈H₈] and (d)[(PPh₃)₂RhSB₉H₁₀], both with η⁴ cluster-to-metal donation.