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http://ir.ncue.edu.tw/ir/handle/987654321/14760
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| Title: | Reversible Carbon-hydrogen Bond Oxidative Addition Across a W—W Multiple Bond |
| Authors: | Chisholm, Malcolm H.;Huang, Jui-Hsien;Huffman, John C. |
| Contributors: | 化學系 |
| Date: | 1997-02
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| Issue Date: | 2012-12-10T01:39:19Z
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| Publisher: | Elsevier |
| 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 O2NWWO2N 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. |
| Relation: | Journal of Organometallic Chemistry, 528(1-2): 221-223 |
| Appears in Collections: | [化學系] 期刊論文
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