Heterometallic cluster complexes (RhMo, RhW) containing bridging 1,2-dicarba-closo-dodecaborane-1,2-dichalocogenolato ligands

Abstract

The 16-electron half-sandwich rhodium complex [Cp*Rh{E₂C₂(B₁₀H₁₀)}] [Cp* = η⁵-C₅Me₅, E = S (1a), Se (1b)] [Cp*Rh{E₂C₂(B₁₀H₁₀)} = η⁵-pentamethylcyclopentadienyl[1,2-dicarba-closo-dodecaborane(12)-dichalcogenolato]rhodium] reacted with Mo(CO)₃(py)₃ in the presence of BF₃·Et₂O in THF solution to afford the {Cp*Rh[E₂C₂(B₁₀H₁₀)]}₂Mo(CO)₂ (E = S (3a); Se (3b)), {Cp*Rh[S₂C₂(B₁₀H₁₀)]}{Mo(CO)₂[S₂C₂(B₁₀H₁₀)]} (4). The voluminous di-tert-butyl substituted Cp half-sandwich rhodium complex [Cp′Rh{E₂C₂(B₁₀H₁₀)}] [E = S (2a), Se (2b)] [Cp′Rh{E₂C₂(B₁₀H₁₀)} = η⁵-(1,3-di(tert-butyl)cyclopentadienyl-[1,2-dicarba-closo-dodecaborane(12)-dichalcogenolato]rhodium) reacted with W(CO)₃(py)₃ in the presence of BF₃·Et₂O in THF solution to give the {Cp′Rh[S₂C₂(B₁₀H₁₀)]}{W(CO)₂[S₂C₂(B₁₀H₁₀)]} (5) and {Cp′Rh[Se₂C₂(B₁₀H₁₀)]}(μ-CO)[W(CO)₃] (6), respectively. The complexes have been fully characterized by IR and NMR spectroscopy as well as by elemental analyses. The X-ray crystal structures of the complexes 3–6 are reported.