Syntheses, structures, and electronic properties of group 5 metal-thiolate complexes that exhibit unusual coordination modes of thiolate ligands have been established. Room-temperature reaction of [Cp*VCl2]3 (Cp∗ = η5-C5Me5) with Na5[B(SCH2S)4] led to the formation of [Cp*VO(SCH2)2S] (1). The solid-state X-ray structure of 1 shows the formation of six-membered l,3,5-trithia-2-vanadacyclohexane that adopted a chair conformation. In a similar fashion, reactions of heavier group 5 precursors [Cp*MCl4] (M = Nb or Ta) with Na5[B(SCH2S)4] yielded bimetallic thiolate complexes [(Cp*M)2(μ-S)μ-C(H)S3-κ2S:κ2S′,S″μ-SC(H)S-κ2C:κ2S,S′′′′] (3a: M = Nb and 3b: M = Ta). One of the key features of molecules 3a and 3b is the presence of square-pyramidal carbon, which is quite unusual. The reactions also yielded bimetallic methanedithiolate complexes [(Cp*Nb)2(μ-S)(μ-SCH2S-κ2S,S′)(μ,η2:η2-BH3S)] (2) and [(Cp*Ta)2(μ-O)(μ-SCH2S-κ2S,S′)(μ-H)μ-S2C(H)SCH2S-κ2S″:κ2S,S′′′′] (4). Complex 2 contains a methanedithiolate ligand that stabilizes the unsaturated niobaborane species. On the other hand, one ((mercaptomethyl)thio)methanedithiolate ligand C2H4S3 is present in 4, which is coordinated to metal centers and exhibits the μ-κ2S″:κ2S,S′′′′ bonding mode. Along with the formation of 3b and 4, the reaction of [Cp*TaCl4] with Na5[B(SCH2S)4] yielded [(Cp*Ta)2(μ-S)μ-(SBS)S(CH2S)2(BH2S)-κ2B:κ2S:κ4S′,S″,S,S′′′′] (5) containing a trithiaborate unit (BS3). Complex 5 consists of pentacoordinate boron that resides in a square-pyramidal environment. All the complexes have been characterized by multinuclear NMR, UV-vis spectroscopy, mass spectrometry, and single-crystal X-ray diffraction studies. Copyright © 2020 American Chemical Society.