title: Sulfur-based redox reactions in Mo3S7(4+) and Mo3S4(4+) clusters bearing halide and 1,2-dithiolene ligands: a mass spectrometric and density functional theory study.
abstract: The gas phase fragmentation reactions of sulfur-rich [Mo(3)S(7)Br(6)](2-) (1(2-)), [Mo(3)S(7)(bdt)(3)](2-) (2(2-)), and [Mo(3)S(4)(bdt)(3)](2-) (3(2-)) (bdt = benzenedithiolate) complexes have been investigated by electrospray ionization (ESI) tandem mass spectrometry and theoretical calculations at the density functional theory level. Upon collision induced dissociation (CID) conditions, the brominated 1(2-) dianion dissociates through two sequential steps that involves a heterolytic Mo-Br cleavage to give [Mo(3)S(7)Br(5)](-) plus Br(-) followed by a two-electron redox process that affords [Mo(3)S(5)Br(5)](-) and diatomic S(2) sulfur. Dianion [Mo(3)S(7)(bdt)(3)](2-) (2(2-)) dissociates through two sequential redox processes evolving diatomic S(2) sulfur and neutral bdt to yield [Mo(3)S(5)(bdt)(3)](2-) and [Mo(3)S(5)(bdt)(2)](2-), respectively. Conversely, dianion [Mo(3)S(4)(bdt)(3)](2-) (3(2-)), with sulfide instead of disulfide S(2)(2-) bridged ligands, remains intact under identical fragmentation conditions, thus highlighting the importance of disulfide ligands (S(2)(2-)) as electron reservoirs to trigger redox reactions. Regioselective incorporation of (34)S and Se at the equatorial position of the Mo(3)S(7) cluster core in 1(2-) and 2(2-) have been used to identify the product ions along the fragmentation pathways. Reaction mechanisms for the gas-phase dissociation pathways have been elucidated by means of B3LYP calculations, and a comparison with the solution reactivity of Mo(3)S(7) and Mo(3)S(4) clusters as well as closely related Mo/S/dithiolene systems is also discussed.
authors.affiliation: Departament de Química Física i Analítica, Universitat Jaume I, Av. Sos Baynat s/n, 12071 Castelló, Spain.
authors.forename: Rosa
authors.initials: R
authors.lastname: Llusar
authors.forename: Victor
authors.initials: V
authors.lastname: Polo
authors.forename: Ederley
authors.initials: E
authors.lastname: Velez
authors.forename: Cristian
authors.initials: C
authors.lastname: Vicent
mesh_terms: D017605:Bromine Compounds / Q000737:chemistry*; D004220:Disulfides / Q000737:chemistry*; D008958:Models, Molecular; D008982:Molybdenum / Q000737:chemistry*; D010084:Oxidation-Reduction; D011789:Quantum Theory; D021241:Spectrometry, Mass, Electrospray Ionization; D013455:Sulfur / Q000737:chemistry
chemical_list: D017605:Bromine Compounds; D004220:Disulfides; D013455:Sulfur; D008982:Molybdenum