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

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

Research output: Contribution to journalArticle

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)22-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 languageEnglish
Pages (from-to)221-223
Number of pages3
JournalJournal of Organometallic Chemistry
Volume528
Issue number1-2
DOIs
Publication statusPublished - 1997 Feb 1

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Hydrocarbons
Pyridine
Hydrogen
Hydrogen bonds
Carbon
Lewis Bases
hydrogen bonds
Temperature
Ethane
carbon
Vacuum
Phenol
Heating
Nuclear magnetic resonance spectroscopy
Phenols
Infrared spectroscopy
Spectrum Analysis
pyridines
hydrocarbons
Chemical activation

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Chisholm, Malcolm H. ; Huang, Jui-Hsien ; Huffman, John C. / Reversible carbon-hydrogen bond oxidative addition across a W-W multiple bond. In: Journal of Organometallic Chemistry. 1997 ; Vol. 528, No. 1-2. pp. 221-223.
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Reversible carbon-hydrogen bond oxidative addition across a W-W multiple bond. / Chisholm, Malcolm H.; Huang, Jui-Hsien; Huffman, John C.

In: Journal of Organometallic Chemistry, Vol. 528, No. 1-2, 01.02.1997, p. 221-223.

Research output: Contribution to journalArticle

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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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