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

Lubin Luo, Giuseppe Lanza, Ignazio L. Fragalà, Charlotte L. Stern, Tobin J Marks

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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)2MO, M = Cr, Mo, W. Efficient, high-yield syntheses of the pairs Cp2MH2/(MeCp)2MH2, Cp2MCl2/(MeCp)2MCl2, and Cp2MO/(MeCp)2MO where M = Mo or W are reported. The molecular structure of (MeCp)2WO features a 'bent sandwich' geometry with a W=O distance of 2.04(1) Å and an average W- C(Cp) distance of 2.371(8) Å. Thus, W-C(Cp) exhibits a ~0.07 Å 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)2MO silanolytic (Me3SiCl, Me3-SiI) 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 π antibonding levels, and a pronounced accumulation of negative charge on the oxo ligand (consistent with observed nucleophilicity of these complexes). Calculated Cp2MCl2 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.

Original languageEnglish
Pages (from-to)3111-3122
Number of pages12
JournalJournal of the American Chemical Society
Volume120
Issue number13
DOIs
Publication statusPublished - Apr 8 1998

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Molecular Structure
Metals
Ligands
Calorimetry
Molecular structure
Geometry
Titration
Population
Elongation
metallocene
Experiments

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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. / Luo, Lubin; Lanza, Giuseppe; Fragalà, Ignazio L.; Stern, Charlotte L.; Marks, Tobin J.

In: Journal of the American Chemical Society, Vol. 120, No. 13, 08.04.1998, p. 3111-3122.

Research output: Contribution to journalArticle

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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)2MO, M = Cr, Mo, W. Efficient, high-yield syntheses of the pairs Cp2MH2/(MeCp)2MH2, Cp2MCl2/(MeCp)2MCl2, and Cp2MO/(MeCp)2MO where M = Mo or W are reported. The molecular structure of (MeCp)2WO features a 'bent sandwich' geometry with a W=O distance of 2.04(1) {\AA} and an average W- C(Cp) distance of 2.371(8) {\AA}. Thus, W-C(Cp) exhibits a ~0.07 {\AA} 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)2MO silanolytic (Me3SiCl, Me3-SiI) 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 π antibonding levels, and a pronounced accumulation of negative charge on the oxo ligand (consistent with observed nucleophilicity of these complexes). Calculated Cp2MCl2 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.",
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T1 - 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

AU - Luo, Lubin

AU - Lanza, Giuseppe

AU - Fragalà, Ignazio L.

AU - Stern, Charlotte L.

AU - Marks, Tobin J

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N2 - 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)2MO, M = Cr, Mo, W. Efficient, high-yield syntheses of the pairs Cp2MH2/(MeCp)2MH2, Cp2MCl2/(MeCp)2MCl2, and Cp2MO/(MeCp)2MO where M = Mo or W are reported. The molecular structure of (MeCp)2WO features a 'bent sandwich' geometry with a W=O distance of 2.04(1) Å and an average W- C(Cp) distance of 2.371(8) Å. Thus, W-C(Cp) exhibits a ~0.07 Å 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)2MO silanolytic (Me3SiCl, Me3-SiI) 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 π antibonding levels, and a pronounced accumulation of negative charge on the oxo ligand (consistent with observed nucleophilicity of these complexes). Calculated Cp2MCl2 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.

AB - 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)2MO, M = Cr, Mo, W. Efficient, high-yield syntheses of the pairs Cp2MH2/(MeCp)2MH2, Cp2MCl2/(MeCp)2MCl2, and Cp2MO/(MeCp)2MO where M = Mo or W are reported. The molecular structure of (MeCp)2WO features a 'bent sandwich' geometry with a W=O distance of 2.04(1) Å and an average W- C(Cp) distance of 2.371(8) Å. Thus, W-C(Cp) exhibits a ~0.07 Å 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)2MO silanolytic (Me3SiCl, Me3-SiI) 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 π antibonding levels, and a pronounced accumulation of negative charge on the oxo ligand (consistent with observed nucleophilicity of these complexes). Calculated Cp2MCl2 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.

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