Cobalt, Rhodium, Iridium, and Ruthenium Carbonyl Complexes with Stanna-closo-dodecaborate: 103Rh NMR, 119Sn Mossbauer Spectroscopy, and Solid-State 119Sn NMR

Depending on the stoichiometry stanna-closo-dodecaborate [SnB11H11](2-) reacts with the dimeric carbonyl complex [Rh(CO)(2)Cl](2) to give a dinuclear rhodium coordination compound with bridging tin ligands, [Et3MeN](6-) [Rh-2(CO)(4)(SnB11H11)(4)] (1), or a pentagonal-bipyramidal complex, [Et4N](5)[Rh(CO)(2)(SnB11H11)(3)] (2), with the carbonyl ligands in axial position. The analogous iridium and cobalt complexes [Et4N](5)[Ir(CO)(2)(SnB11H11)(3)] (3) and [Me4N](5-) [Co(CO)(2)(SnB11H11)(3)] (4) exhibit a pentacoordinated structure with the tin ligands in axial positions. The dimeric ruthenium chlorocarbonyl complex [Ru(CO)(3)Cl-2](2) reacts with four equivalents of the tin nucleophile to give the octahedrally coordinated ruthenium complex [Et3MeN](4)[Ru-cis-(CO)(2)-cis-Cl-2-trans-(SnB11H11)(2)] (5). The synthesized coordination compounds were characterized by X-ray crystal structure analysis, by Rh-103, Sn-119, and B-11 NMR spectroscopy in solution, and in the case of the rhodium complexes 1 and 2 by Sn-119 solid-state NMR and Sn-119 Mossbauer spectroscopy.