Reversible carbon-hydrogen bond oxidative addition across a W-W multiple bond

Malcolm H. Chisholm; Jui Hsien Huang; John C. Huffman

doi:10.1016/S0022-328X(96)06597-7

Reversible carbon-hydrogen bond oxidative addition across a W-W multiple bond

Malcolm H. Chisholm, Jui Hsien Huang, John C. Huffman

Department of Chemistry

Research output: Contribution to journal › Article

8 Citations (Scopus)

Abstract

As previously reported, the reaction between W₂(NMe₂)₆ and 2,2′-methylenebis(6-tert-butyl-4-methyl-phenol), HO-CH₂-OH, in hydrocarbon solvents leads to W₂( μ-H)( μ-NMe₂)(η²-O-CH₂-O)(η³-O-CH-O)(HNMe₂)(NMe₂), 1, by oxidative cyclometallation to the ditungsten center. Upon heating 1 to greater than 60°C under dynamic vacuum W₂(NMe₂)₂(η²-O-CH₂-O)₂,2, is formed with elimination of HNMe₂. Compound 2 is proposed to have an ethane-like O₂NW≡WO₂N core based on NMR data. Addition of HNMe₂ to 2 at room temperature converts 2 to 1. The addition of other neutral ligands (pyridine, PMe₃) to hydrocarbon solutions of 2 promotes the C-H oxidative addition to the W₂ center and the pyridine adduct W₂( μ-H)( μ-NMe₂)(NMe₂)(py)(η²-O-CH₂-O)(η³-O-CH-O), 3, has been fully characterized by an X-ray study. Addition of PMe₃ to 2 at low temperatures reveals that Lewis base association occurs prior to C-H activation. There is no evidence for an agostic interaction for 2 by NMR or IR spectroscopy.

Original language	English
Pages (from-to)	221-223
Number of pages	3
Journal	Journal of Organometallic Chemistry
Volume	528
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(96)06597-7
Publication status	Published - 1997 Feb 1

All Science Journal Classification (ASJC) codes

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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Chisholm, M. H., Huang, J. H., & Huffman, J. C. (1997). Reversible carbon-hydrogen bond oxidative addition across a W-W multiple bond. Journal of Organometallic Chemistry, 528(1-2), 221-223. https://doi.org/10.1016/S0022-328X(96)06597-7

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abstract = "As previously reported, the reaction between W2(NMe2)6 and 2,2′-methylenebis(6-tert-butyl-4-methyl-phenol), HO-CH2-OH, in hydrocarbon solvents leads to W2( μ-H)( μ-NMe2)(η2-O-CH2-O)(η3-O-CH-O)(HNMe2)(NMe2), 1, by oxidative cyclometallation to the ditungsten center. Upon heating 1 to greater than 60°C under dynamic vacuum W2(NMe2)2(η2-O-CH2-O)2,2, is formed with elimination of HNMe2. Compound 2 is proposed to have an ethane-like O2NW≡WO2N core based on NMR data. Addition of HNMe2 to 2 at room temperature converts 2 to 1. The addition of other neutral ligands (pyridine, PMe3) to hydrocarbon solutions of 2 promotes the C-H oxidative addition to the W2 center and the pyridine adduct W2( μ-H)( μ-NMe2)(NMe2)(py)(η2-O-CH2-O)(η3-O-CH-O), 3, has been fully characterized by an X-ray study. Addition of PMe3 to 2 at low temperatures reveals that Lewis base association occurs prior to C-H activation. There is no evidence for an agostic interaction for 2 by NMR or IR spectroscopy.",

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N2 - As previously reported, the reaction between W2(NMe2)6 and 2,2′-methylenebis(6-tert-butyl-4-methyl-phenol), HO-CH2-OH, in hydrocarbon solvents leads to W2( μ-H)( μ-NMe2)(η2-O-CH2-O)(η3-O-CH-O)(HNMe2)(NMe2), 1, by oxidative cyclometallation to the ditungsten center. Upon heating 1 to greater than 60°C under dynamic vacuum W2(NMe2)2(η2-O-CH2-O)2,2, is formed with elimination of HNMe2. Compound 2 is proposed to have an ethane-like O2NW≡WO2N core based on NMR data. Addition of HNMe2 to 2 at room temperature converts 2 to 1. The addition of other neutral ligands (pyridine, PMe3) to hydrocarbon solutions of 2 promotes the C-H oxidative addition to the W2 center and the pyridine adduct W2( μ-H)( μ-NMe2)(NMe2)(py)(η2-O-CH2-O)(η3-O-CH-O), 3, has been fully characterized by an X-ray study. Addition of PMe3 to 2 at low temperatures reveals that Lewis base association occurs prior to C-H activation. There is no evidence for an agostic interaction for 2 by NMR or IR spectroscopy.

AB - As previously reported, the reaction between W2(NMe2)6 and 2,2′-methylenebis(6-tert-butyl-4-methyl-phenol), HO-CH2-OH, in hydrocarbon solvents leads to W2( μ-H)( μ-NMe2)(η2-O-CH2-O)(η3-O-CH-O)(HNMe2)(NMe2), 1, by oxidative cyclometallation to the ditungsten center. Upon heating 1 to greater than 60°C under dynamic vacuum W2(NMe2)2(η2-O-CH2-O)2,2, is formed with elimination of HNMe2. Compound 2 is proposed to have an ethane-like O2NW≡WO2N core based on NMR data. Addition of HNMe2 to 2 at room temperature converts 2 to 1. The addition of other neutral ligands (pyridine, PMe3) to hydrocarbon solutions of 2 promotes the C-H oxidative addition to the W2 center and the pyridine adduct W2( μ-H)( μ-NMe2)(NMe2)(py)(η2-O-CH2-O)(η3-O-CH-O), 3, has been fully characterized by an X-ray study. Addition of PMe3 to 2 at low temperatures reveals that Lewis base association occurs prior to C-H activation. There is no evidence for an agostic interaction for 2 by NMR or IR spectroscopy.

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