Reactivity of [(Cp*CoPh)(Cp*Co)(μ-TePh)(μ-k 2 -Te,H-TeBH 3 )] Toward [ M (CO) 5 ·THF] ( M = Mo and W), CS 2 , and [Fe 2 (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-k 2 -Te,H-TeBH 3 )] ( 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 BH 3 . 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 CS 2 . 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-S 3 TeS 3 -κ 2 S:κ 2 Te:κ 2 S')] ( 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 [Fe 2 (CO) 9 ]. However, the reaction led to the formation of the trimetallic complex [Cp*Co(CO)(μ 3 -Te) 2 {Fe 2 (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.