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Chemistry of molybdenum part 7. reactivity of terminal oxo ligands in cis moo 2acda 2 hacda equals 2 aminocyclopent 1 ene 1 carbodithioic acid toward proton and electron donor reagents synthesis redox chemistry and spectroscopic characterization of neutral seven coordinate catecholato and aryldiazenido compounds of molybdenum



Chemistry of molybdenum part 7. reactivity of terminal oxo ligands in cis moo 2acda 2 hacda equals 2 aminocyclopent 1 ene 1 carbodithioic acid toward proton and electron donor reagents synthesis redox chemistry and spectroscopic characterization of neutral seven coordinate catecholato and aryldiazenido compounds of molybdenum



Journal of the Chemical Society Dalton Transactions (8): 2169-2174



The reactivity of co-ordinated oxo-ligands in cis-[MoO2(acda)2] (Hacda = 2-aminocyclopent-1-ene-1-carbodithioic acid) toward proton- and electron-donor reagents has been investigated. Molybdenum(VI) compounds [MoO(L)(acda)2] (L = catecholate, 2a; 4-tert-butylcatecholate, 2b; 3,5-di-tert-butylcatecholate, 2c; naphthalene-2,3-diolate, 2d; or tetrachlorocatecholate, 2e) are obtained when catechols are used for oxo abstraction. Substituted phenylhydrazines on the other hand form non-oxodiazenido complexes [Mo(N2C6H4X-p) (acda)3] (X = H, 3a; Me, 3b; or Cl, 3c). The compounds have been characterized by electronic, IR and ESR spectoscopy and electrochemistry. In the visible region the electronic spectra are dominated by a strong ligand-to-metal charge-transfer (l.m.c.t.) band for both series of compounds. Their electrochemistry has been studied in dimethylformamide at a platinum electrode. For the catecholato compounds 2a-2e a metal-based reduction (MoVI-MoV, Epc) and a ligand-based oxidation (Epa) each involving a single electron are observed. Substituents in the catecholato ring have a significant influence on the energy of the l.m.c.t. transitions (Eop) as well as on Epc and Epa. A linear relationship exists between Eop and .DELTA.E(redox) where .DELTA.E(redox) = Epc - Epa. The oxidised species derived from the 0/1 + redox couple ofthe diazenido series 3a-3c are ESR active with hyperfine spectra due to 95,97Mo and 14N couplings. The electron-transfer orbital in this case is believed to be metal based with sufficient mixing from the diazenido nitrogen orbital.

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