期刊
JOURNAL OF ORGANOMETALLIC CHEMISTRY
卷 694, 期 4, 页码 551-560出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jorganchem.2008.10.047
关键词
Allylic rearrangement; Cationic; Gold; N-Heterocyclic carbene; Pyridine
资金
- Ministerio de Educacion y Ciencia (Spain)
- ICIQ Foundation
- ICREA
- AGAUR [2007FI_A01466]
- Umicore
The reaction of [(NHC) AuCl] complexes (NHC = N-heterocyclic carbene) with a chloride abstractor of the type AgX, where X is a non-coordinating anion, led, in the presence of a neutral coordinating solvent S, to a series of cationic gold(I) complexes of formulae [(NHC)Au(S)] X. Hence, different cationic NHC-gold(I) species bound to acetonitrile, pyridine, 2-Br-pyridine, 3-Br-pyridine, norbornadiene, and THF could be synthesized and characterized by H-1 and C-13 NMR spectroscopies. Among these, the results of X-ray diffraction studies for [(IPr)Au(NCMe)]SbF6, [(IAd)Au(NCMe)]PF6, [(IPr)Au(pyr)]PF6, [(IPr) Au(2-Br-pyr)]PF6, [(IPr)Au(3-Br-pyr)]PF6 are discussed. As special feature, the structure of [(IPr)Au(2-Br-pyr)] PF6 presented a secondary interaction between the gold and bromine atoms. Additionally, while attempting to obtain crystals of [(IPr)Au(nbd)]PF6, we crystallized a decomposition product featuring a very rare PF4- anion as bridging ligand with formulae [(mu-PF4)((IPr)Au)(2)]PF4. The observation of a possible P-F bond activation has important implications for cationic Au-based homogeneous catalysis. Finally, we compared the catalytic activities of the different cationic [(NHC) Au(S)] X complexes in the allylic acetate rearrangement reaction and notably observed the inertness of pyridine-based catalysts. (C) 2008 Elsevier B.V. All rights reserved.
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