Reactivity of [(Cp*CoPh)(Cp*Co)(μ-TePh)(μ-k²-Te,H-TeBH₃)] Toward [M(CO)₅·THF] (M = Mo and W), CS₂, and [Fe₂(CO)₉]

Syntheses and structural elucidation of homo- and heterochalcogen-bridged complexes of cobalt are described. The photolytic reaction of bimetallic hydridoborate species [(Cp*CoPh)(Cp*Co)(μ-TePh)(μ-k2-Te,H-TeBH3)] (1) in the presence of [M(CO)5·THF] (M = Mo and W) afforded unprecedented tellurolate-bridged [(Cp*Co)2(μ-TePh)3]+[TePh{M(CO)5}2]− (M = Mo (2), W (3)) as ionic complexes with the release of BH3. Complex 2 has three bridged-TePh moieties between two Cp*Co fragments in the cation part, whereas the anionic part, [TePh{M(CO)5}2]−, shows a distorted trigonal pyramidal core. In order to synthesize mixed chalcogenate-bridged complexes having both S and Te, we carried out the photolytic reaction of 1 with CS2. Although the objective of generating mixed chalcogen-bridged complex [(Cp*Co)2(μ-TePh)2(μ-S)] was not achieved, the reaction yielded an unusual bimetallic thiotellurite complex [(Cp*Co)2(μ-S3TeS3-κ2S:κ2Te:κ2S′)] (4). Complex 4 has two wings, each consisting of three sulfur atoms, that are connected to two Co-atoms and one Te-atom. Further, to synthesize the Fe analogue of 2 and 3, a similar reaction was carried out with [Fe2(CO)9]. However, the reaction led to the formation of the trimetallic complex [Cp*Co(CO)(μ3-Te)2{Fe2(CO)6}] (5). These complexes were characterized by employing different multinuclear NMR, IR spectroscopies, single-crystal X-ray diffraction analyses, and mass spectrometry. Additionally, computational analyses of these chalcogen-bridged neutral and ionic complexes were conducted to offer insight into their bonding.