This talk will provide the results of extensive experimental mechanistic investigations of N-N bond cleavage pathways for the titled complexes that occur under thermal conditions for group 5 metal derivatives and via photolysis for group 6 metal analogs to provide the corresponding dinuclear bis(-nitrido) complexes, {(?5-C5Me5)M[N(i-Pr)C(X)N(i-Pr)](�-N)}2, in each case except for M = V. Results from detailed kinetic and crossover experiments for M = Nb and Ta will be discussed. In the case of M = Mo and W, quantitative N-atom functionalization chemistry has been developed that provides access to the corresponding mononuclear group 6 imido complexes, (?5-C5Me5)M[N(i-Pr)C(X)N(i-Pr)](NR), that can engage in catalytic imido group transfer reactions. Finally, a discussion of remaining obstacles that must still be overcome to achieve catalytic dinitrogen fixation using the present metals and supporting ligand environment will be presented.

Investigation of mechanistic pathways for N-N bond cleavage with group 5 and 6 dinuclear pentamethylcyclopentadienyl amidinate dinitrogen complexes of general formula, {(?5-C5Me5)M[N(i-Pr)C(X)N(i-Pr)]}2(�-?1:?1-N2), for M = V, Nb, Ta, Mo and W

247th National Meeting (2014)

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