Journal of Chemical Physics, Vol.106, No.20, 8504-8515, 1997
An Ab-Initio Study of the Reaction-Mechanism of Co++nh3
To investigate the mechanism for N-H bond activation by a transition metal, the reactions of Co+(F-3,F-5) With NH3 have been studied with complete active space self-consistent field (CASSCF), multireference configuration interaction (MR-SDCI), and multireference many body perturbation theory (MRMP) wave functions, using both effective core potential and all-electron methods. Upon their initial approach, the reactants yield an ion-molecule complex, CoNH3+(E-3,(5)A(2),(5)A(1)), With retention of C-3v symmetry. The Co+=NH3 binding energies are estimated to be 49 (triplet) and 45 (quintet) kcal/mol. Subsequently, the N-H bond is activated, leading to an intermediate complex H-Co-NH2+ (C-2v symmetry), through a three-center transition state with an energy barrier of 56-60 (triplet) and 70-73 (quintet) kcal/mol. The energy of H-Co-NH2+, relative to that of CoNH3+, is estimated to be 60 to 61 (triplet) and 44 (quintet) kcal/mol. However, the highest levels of theory employed here (including dynamic correlation corrections) suggest that the triplet intermediate HCoNH2+ may not exist as a minimum on the potential energy surface. Following Co-N or H-Co bond cleavage, the complex H-Co-NH2+ leads to HCo++NH2 or H+CoNH2+. Both channels (triplet and quintet) are found to be endothermic by 54-64 kcal/mol.
Keywords:TRANSITION-METAL CARBENE;DEGENERATE PERTURBATION-THEORY;COMPACT EFFECTIVE POTENTIALS;EXPONENT BASIS-SETS;C BOND ACTIVATION;SPACE SCF METHOD;ELECTRONIC-STRUCTURE;GEOMETRIC STRUCTURES;HIGH-VALENT;GAS-PHASE