期刊
ORGANOMETALLICS
卷 30, 期 11, 页码 3182-3193出版社
AMER CHEMICAL SOC
DOI: 10.1021/om200291s
关键词
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资金
- NSF [CHE-0555425]
- NCBC [2008-IDG-1010]
- Duke University
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0911265] Funding Source: National Science Foundation
A family of cationic gold pi-diene complexes of the form {[P(t-Bu)(2)o-biphenyl]Au(eta(2)-diene)}+SbF6- were isolated in >80% yield from reaction of various dienes with a mixture of [P(t-Bu)(2)o-biphenyl]AuCl and AgSbF6 and were characterized by spectroscopy and, in four cases, by X-ray crystallography. Solution and solid-state analysis of these complexes established selective binding of gold to the less substituted C=C bond of the diene in the case of dienes that possessed differentially substituted C=C bonds. C-13 NMR analysis and evaluation of the relative binding affinities of substituted dienes point to a bonding model in which the gold alkene interaction is stabilized via donation of electron density from the uncomplexed C=C bond to the complexed C=C bond of the diene. Variable-temperature NMR analysis of gold pi-diene complexes revealed fluxional behavior consistent with facile (Delta G(double dagger) = 9.6-11.9 kcal mol(-1)) intramolecular exchange of the complexed and uncomplexed C=C bonds of the diene ligand.
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