In this paper, we report a synthetic; molecular structure, thermochemical, and ab initio Hartree-Fock/Moller-Plesset level study of bonding and bonding energetics in the group 6 metallocene oxo series Cp2Mo/(MeCp)(2)MO, M = Cr, Mo, W. Efficient, high-yield syntheses of the pairs Cp2MH2/(MeCp)(2)MH2, Cp2MCl2/(MeCp)(2)MCl2, and Cp2MO/(MeCp)(2)MO where M = Mo or W are reported. The molecular structure of (MeCp)(2)WO features a "bent sandwich" geometry with a W=O distance of 2.04(1) Angstrom and an average W-C(Cp) distance of 2.371(8) Angstrom. Thus, W-C(Cp) exhibits a similar to 0.07 Angstrom elongation over the corresponding distance in typical Cp2WX2 complexes and a W=O distance which appears to be elongated versus what might be expected for a formal triple bond. D(M=O) values obtained from (MeCp)(2)MO silanolytic (Me3SiCl, Me2SiI) batch titration calorimetry are very large: 110(11) kcal/mol (M = Mo) and 132(10) kcal/mol (M = W). The corresponding D(W-OTMS) value is determined to be 65(18) kcal/mol. Ab initio relativistic core potential calculations reveal significantly weakened M-Cp bonding versus that in the corresponding Cp2MCl2 compounds, weakened M=O bonding due to population of M-O st antibonding levels, and a pronounced accumulation of negative charge on the oxo ligand (consistent with observed nucleophilicity of these complexes). Calculated Cp(2)MCh and Cp2MO molecular geometries and D(M=O) values at the MP2 level are in favorable agreement with experiment. The D(M=O) and D(M-O) data provide significant insight into the chemistry of Cp2MO complexes, especially in regard to constraints on oxo transfer as well as oxametallacycle formation and scission processes.
Energetics of metal-ligand multiple bonds. A combined solution thermochemical and ab initio quantum chemical study of M=O bonding in group 6 metallocene oxo complexes
LANZA, GIUSEPPE;
1998-01-01
Abstract
In this paper, we report a synthetic; molecular structure, thermochemical, and ab initio Hartree-Fock/Moller-Plesset level study of bonding and bonding energetics in the group 6 metallocene oxo series Cp2Mo/(MeCp)(2)MO, M = Cr, Mo, W. Efficient, high-yield syntheses of the pairs Cp2MH2/(MeCp)(2)MH2, Cp2MCl2/(MeCp)(2)MCl2, and Cp2MO/(MeCp)(2)MO where M = Mo or W are reported. The molecular structure of (MeCp)(2)WO features a "bent sandwich" geometry with a W=O distance of 2.04(1) Angstrom and an average W-C(Cp) distance of 2.371(8) Angstrom. Thus, W-C(Cp) exhibits a similar to 0.07 Angstrom elongation over the corresponding distance in typical Cp2WX2 complexes and a W=O distance which appears to be elongated versus what might be expected for a formal triple bond. D(M=O) values obtained from (MeCp)(2)MO silanolytic (Me3SiCl, Me2SiI) batch titration calorimetry are very large: 110(11) kcal/mol (M = Mo) and 132(10) kcal/mol (M = W). The corresponding D(W-OTMS) value is determined to be 65(18) kcal/mol. Ab initio relativistic core potential calculations reveal significantly weakened M-Cp bonding versus that in the corresponding Cp2MCl2 compounds, weakened M=O bonding due to population of M-O st antibonding levels, and a pronounced accumulation of negative charge on the oxo ligand (consistent with observed nucleophilicity of these complexes). Calculated Cp(2)MCh and Cp2MO molecular geometries and D(M=O) values at the MP2 level are in favorable agreement with experiment. The D(M=O) and D(M-O) data provide significant insight into the chemistry of Cp2MO complexes, especially in regard to constraints on oxo transfer as well as oxametallacycle formation and scission processes.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.