title: Comparative kinetics and mechanism of oxygen and sulfur atom transfer reactions mediated by bis(dithiolene) complexes of molybdenum and tungsten.
abstract: Although the kinetics and mechanism of metal-mediated oxygen atom (oxo) transfer reactions have been examined in some detail, sulfur atom (sulfido) transfer reactions have not been similarly scrutinized. The reactions [M(IV)(O-p-C(6)H(4)X')(S(2)C(2)Me(2))(2)](1-) + Ph(3)AsQ --> [M(VI)Q(O-p-C(6)H(4)X')(S(2)C(2)Me(2))(2)](1-) + Ph(3)As (M = Mo, W; Q = O, S) with variable substituent X' have been investigated in acetonitrile in order to determine the relative rates of oxo versus sulfido transfer at constant structure (square pyramidal) of the atom acceptor and of atom transfer at constant structure of the atom donor and metal variability of the atom acceptor. All reactions exhibit second-order kinetics and entropies of activation (-25 to -45 eu) consistent with an associative transition state. At parity of atom acceptor, k(2)(S) (0.25-0.75 M(-1)s(-1)) > k(2)(O) (0.023-0.060 M(-1)s(-1)) with M = Mo and k(2)(S) (4.1-66.7 M(-1)s(-1)) > k(2)(O) (1.8-9.8 M(-1)s(-1)) with M = W. At constant atom donor and X', k(2)(W) > k(2)(Mo) with reactivity ratios k(2)(W)/k(2)(Mo) = 78-184 (Q = O) and 16-89 (Q = S). Rate constants refer to 298 K. At constant M and Q, rates increase in the order X' = Me less, similar OMe < H < Br < COMe < CN; increasing electron-withdrawing propensity accelerates reaction rates. The probable transition state involves significant Ph(3)AsQ...M bond-making (X' rate trend) and concomitant As-Q bond weakening (bond energy order As-O > As-S). Orders of oxo and sulfido donor ability of substrates and complexes are deduced on the basis of qualitative reactivity properties determined here and elsewhere. This work complements previous studies of the reaction systems [M(IV)(O-p-C(6)H(4)X')(S(2)C(2)Me(2))(2)](1-)/XO where the substrates are N-oxides and S-oxides and k(2)(W) > k(2)(Mo) at constant substrate also applies. The reaction order of substrates is Me(3)NO > (CH(2))(4)SO > Ph(3)AsS > Ph(3)AsO. This research provides the first quantitative information of metal-mediated sulfido transfer.
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
authors.forename: Jun-Jieh
authors.initials: JJ
authors.lastname: Wang
authors.forename: Olga P
authors.initials: OP
authors.lastname: Kryatova
authors.forename: Elena V
authors.initials: EV
authors.lastname: Rybak-Akimova
authors.forename: R H
authors.initials: RH
authors.lastname: Holm
mesh_terms: D018360:Crystallography, X-Ray; D007506:Iron-Sulfur Proteins / Q000737:chemistry*; D007700:Kinetics; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010088:Oxidoreductases / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry*; D014414:Tungsten / Q000737:chemistry*
chemical_list: D007506:Iron-Sulfur Proteins; D009942:Organometallic Compounds; D013455:Sulfur; D008982:Molybdenum; D010088:Oxidoreductases; C045664:dimethyl sulfoxide reductase; D010100:Oxygen; D014414:Tungsten