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Volumn 461-462, Issue , 1999, Pages 167-175

Theoretical studies on π-complex formation of organocopper compounds with acetylene. The origin of nucleophilicity of organocuprates

Author keywords

complex; Acetylene; Copper 3d orbital participation; Electron correlation; Me2Au ; Me2Cu ; Organocuprate(I) complex

Indexed keywords

ACETYLENE; COPPER DERIVATIVE;

EID: 0033515415     PISSN: 01661280     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0166-1280(98)00458-8     Document Type: Article
Times cited : (19)

References (81)
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    • - addition to acetylene, the geometries of complex, TS as well as the activation energy were found to be unaffected (<1.2% for geometry and 0.3 kcal/mol for energy) by addition of a diffuse sp function of exponent α=0.438 for carbon (T. Clark, J. Chandrasekhar, G.W. Spitznagel, P.v.R. Schleyer, J. Comput. Chem. 4 (1983) 294).
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    • The B3LYP complex formation energies are closer to the CCSD(T) energies (-1.4 kcal/mol, Refs. [39-41]) than the MP2 one of -8.6 kcal/mol, since BHandHLYP/631A method too much underestimates the complex formation energy (+7.4 kcal/mol unstable than reactants). As to BHandH (Becke Half-and-Half), see: A.D. Becke, J. Chem. Phys. 98 (1993) 1372.
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    • Boys and Bernardi's correction of basis set super position error (57.8 kcal/mol at the B3LYP/631A level and 52.1 kcal/mol at the MP2/631A level) much overestimates the effects due to short C(acetylene)-Cu bond. See: S.F. Boys, F. Bernardi, Mol. Phys. 19 (1970) 553.
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    • Hartree-Fock canonical orbitals and Kohn-Sham orbitals are based on different concepts but they can be qualitatively compared. See
    • Hartree-Fock canonical orbitals and Kohn-Sham orbitals are based on different concepts but they can be qualitatively compared. See: E.J. Baerands, O.V. Gritsenko, J. Phys. Chem. A 30 (1997) 5383.
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    • 2CuLi dimer) because of the presence of lithium cation which neutralizes the charge. HOMO energy at the B3LYP/631A//B3LYP level is positive (+0.33 eV). Discussions on the physical problem for the positive HOMO energy of anionic system see
    • 2CuLi dimer) because of the presence of lithium cation which neutralizes the charge. HOMO energy at the B3LYP/631A//B3LYP level is positive (+0.33 eV). Discussions on the physical problem for the positive HOMO energy of anionic system see: J.M. Galbraith, H.F. Schaefer III, J. Chem. Phys. 105 (1996) 862.
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    • The tendency that B3LYP occupied orbitals show higher orbital energies than HF has already been reported in the literature
    • The tendency that B3LYP occupied orbitals show higher orbital energies than HF has already been reported in the literature. U. Salzner, J.B. Lagnowski, P.G. Pickup, R.A. Poirier, J. Comp. Chem, 18 (1997) 1943.
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    • 2 pair correlation energy of -0.0190 hartree is the largest
    • 2 pair correlation energy of -0.0190 hartree is the largest.


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