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 | |
| Publication status | Published - 1997 Feb 1 |
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All Science Journal Classification (ASJC) codes
- Biochemistry
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry
- Materials Chemistry
Cite this
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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 journal › Article
TY - JOUR
T1 - Reversible carbon-hydrogen bond oxidative addition across a W-W multiple bond
AU - Chisholm, Malcolm H.
AU - Huang, Jui-Hsien
AU - Huffman, John C.
PY - 1997/2/1
Y1 - 1997/2/1
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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UR - http://www.scopus.com/inward/citedby.url?scp=0031067295&partnerID=8YFLogxK
U2 - 10.1016/S0022-328X(96)06597-7
DO - 10.1016/S0022-328X(96)06597-7
M3 - Article
AN - SCOPUS:0031067295
VL - 528
SP - 221
EP - 223
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
IS - 1-2
ER -