Directed Syntheses of CS₂- and CS₃-Bridged Decaborane-14 Analogues

To establish a procedure for single-cage cluster expansion of open cage dimetallaoctaboranes(12), we have investigated the chemistry of nido-[(Cp*M)₂B₆H₁₀] (η⁵-C₅Me₅ = Cp*, 1: M = Co; 2: M = Rh), with diverse chalcogen-based borate ligands. As a result, treatment of nido-1 and nido-2 with Li[BH₂E₃] (E = S, Se, or Te) yielded 10-vertex nido-[(Cp*Co)₂B₇EH₉] (3: E = S; 4: E = Se; 5: E = Te) along with known 10-vertex nido-[(Cp*M)₂B₆H₆E₂] (6: E = S, M = Co; 7: E = Se, M = Co; 8: E = Te, M = Co; 9: E = Se, M = Rh). The geometries of dimetallachalcogenaboranes, 3-9, are isostructural with decaborane(14). Thermolysis of nido-1 and nido-2 with an intermediate, generated from CS₂ and [LiBH₄]·THF reaction in THF, produced nido-[(Cp*M)₂B₆S₂H₄(CH₂S₂)] (10: M = Co; 11: M = Rh) and nido-[(Cp*M)₂B₆S₂H₄(CS₃)] (12: M = Co; 13: M= Rh). Clusters 10-13 are rare species in which one of the B-B bonds is coordinated with a {CS₂}^2- or {CS₃}^2- ligand, generating di(thioborolane) {B₂S₂CH₂} or di(thioboralane)-thione {B₂CS₃} moieties. To examine further the coordination chemistry of CS₂-bridged decaborane(14) analogue nido-10, photolysis was carried out with {M(CO)₅·THF} (M = Mo or W) that led to the isolation of [(Cp*Co)₂B₆S₂H₄(CH₂S₂){M(CO)₅}] (14: M = Mo; 15: M = W), where the {CH₂S₂} moiety is coordinated with one {M(CO)₅} moiety in η¹-fashion. All the synthesized clusters have been characterized by ESI-mass, multinuclear NMR spectroscopy, and IR spectroscopy and structurally solved by single-crystal XRD. Furthermore, DFT calculations probe the bonding of these CS₂- and CS₃-bridged decaborane analogues.