Syntheses, structures, and electronic properties of group 5 metalthiolate complexes that exhibit unusual coordination modes of thiolate ligands have been established. Room-temperature reaction of [Cp*VCl2](3) (Cp* = eta(5)-C5Me5) with Na-5[B(SCH2S)(4)] led to the formation of [Cp*VO{(SCH2)(2)S}] (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 Na-5[B(SCH2S)(4)] yielded bimetallic thiolate complexes [(Cp*M)2(mu-S){mu-C(H)S-3-kappa S-2:kappa S-2''',S''''}{mu-SC(H)S-kappa C-2:kappa S-2',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)(mu-S)(mu-SCH2S-kappa S-2,S')(mu,kappa(2):kappa(2)-BH3S)] (2) and [(Cp*Ta)(2)(mu-O)(mu-SCH2S-kappa S-2,S')(mu-H){mu-S2C(H)SCH2S-kappa S-2 '':kappa S-2''',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 {mu-kappa S-2':kappa S-2',S''''} bonding mode. Along with the formation of 3b and 4, the reaction of [Cp*TaCl4] with Na-5[B(SCH2S)(4)] yielded [(Cp*Ta)(2)(mu-S){mu-(SBS)S(CH2S)2(BH2S)-kappa B-2:kappa S-2:kappa S-4',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, UVvis spectroscopy, mass spectrometry, and single-crystal X-ray diffraction studies.