647858-92-2Relevant academic research and scientific papers
Comparison of thermodynamic and kinetic aspects of oxidative addition of PhE-EPh (E = S, Se, Te) to Mo(CO)3(PR3)2, W(CO)3(PR3)2, and Mo(N[tBu]Ar) 3 complexes. The role of oxidation state and ancillary ligands in metal complex induced chalcogenyl radical generation
McDonough, James E.,Weir, John J.,Sukcharoenphon, Kengkaj,Hoff, Carl D.,Kryatova, Olga P.,Rybak-Akimova, Elena V.,Scott, Brian L.,Kubas, Gregory J.,Mendiratta, Arjun,Cummins, Christopher C.
, p. 10295 - 10303 (2007/10/03)
Enthalpies of oxidative addition of PhE-EPh (E = S, Se, Te) to the M(0) complexes M(PiPr3)2- (CO)3 (M = Mo, W) to form stable complexes M(?EPh)(Pir 3)2(CO)3 are reported and compared to analogous data for addition to the Mo(III) complexes Mo(N[tBu]Ar)3 (Ar = 3,5-C6H3Me2) to form diamagnetic Mo(IV) phenyl chalcogenide complexes Mo(N[tBu]Ar)3(EPh). Reactions are increasingly exothermic based on metal complex, Mo(P iPr3)2(CO)3 iPr3)2(CO)3 tBu]Ar)3, and in terms of chalcogenide, PhTe-TePh 0M-EPh bond strengths, which are used to estimate the energetics of production of a free ?EPh radical when a dichalcogenide interacts with a specific metal complex. To test these data, reactions of Mo(N[tBu]Ar) 3 and Mo(PiPr3)2(CO)3 with PhSe-SePh were studied by stopped-flow kinetics. First- and second-order dependence on metal ion concentration was determined for these two complexes, respectively, in keeping with predictions based on thermochemical data. ESR data are reported for the full set of bound chalcogenyl radical complexes (PhE ?)M(PiPr3)2(CO)3; g values increase on going from S to Se, to Te, and from Mo to W. Calculations of electron densities of the SOMO show increasing electron density on the chalcogen atom on going from S to Se to Te. The crystal structure of W( ?TePh)(PiPr3)2(CO)3 is reported.
Benzonitrile extrusion from molybdenum(IV) ketimide complexes obtained via radical C-E (E = O, S, Se) bond formation: Toward a new nitrogen atom transfer reaction
Mendiratta, Arjun,Cummins, Christopher C.,Kryatova, Olga P.,Rybak-Akimova, Elena V.,McDonough, James E.,Hoff, Carl D.
, p. 4881 - 4891 (2007/10/03)
Beta-elimination is explored as a possible means of nitrogen-atom transfer into organic molecules, Molybdenum(IV) ketimide complexes of formula (Ar[t-Bu]N)3Mo(N=C(X)Ph), where Ar = 3,5-Me2C 6H3 and X = SC6
Molybdenum Chalcogenobenzimidato Complexes: Radical Synthesis and Nitrile Extrusion via β-EPh (E = S, Se, and Te) Elimination
Mendiratta, Arjun,Cummins, Christopher C.,Kryatova, Olga P.,Rybak-Akimova, Elena V.,McDonough, James E.,Hoff, Carl B.
, p. 8621 - 8623 (2008/10/09)
Molybdenum chalcogenobenzimidates of formula (Ph[PhE]C=N)-Mo(N[t-Bu]Ar)3 (Ar = 3,5-C6H 3Me2) have been obtained by treatment of Mo(N[t-Bu]Ar)3 sequentially with benzonitrile and 0.5 equiv of PhEEPh (E = S, Se, and Te). Molecular structure determinations have been carried out for the S and Se variants. The Te variant extrudes PhCN forming structurally characterized (PhTe)Mo(N[t-Bu]Ar)3 with facility assessed via stopped-flow kinetic measurements, while the Se and S analogues exhibit increasing stability. Quantum chemical calculations and solution calorimetry have been employed as an aid to interpretation of the PhCN extrusion reaction.
