Ion pairing in NHC gold(I) olefin complexes: A combined experimental/theoretical study

被引：38

作者：

Salvi, Nicola ^{[1
]}

Belpassi, Leonardo ^{[1
]}

Zuccaccia, Daniele ^{[1
]}

Tarantelli, Francesco ^{[1
]}

Macchioni, Alceo ^{[1
]}

机构：

[1] Univ Perugia, Dipartimento Chim, I-06123 Perugia, Italy

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2010年 / 695卷 / 24期

关键词：

Ion pairing; NOE; NMR; DFT; N-heterocyclic carbenes; Gold-alkene complexes; STRUCTURAL-CHARACTERIZATION; COUNTERION; HYDROAMINATION; RUTHENIUM(II); AGGREGATION; MECHANISM; MODEL; CYCLOISOMERIZATION; APPROXIMATION; SUBSTITUENTS;

D O I：

10.1016/j.jorganchem.2010.08.035

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The relative anion-cation orientation in [(NHC) Au(alkene)] BF4 ion pairs [NHC _ N-Heterocyclic Carbene 1,3-bis(di-iso-propylphenyl)-imidazol-2-ylidene (IPr) and 4,5-dimethyl-N, N'-bis(2,6-diiso-propylphenyl)- imidazol-2-ylidene ((IPr)-I-Me); alkene 4-methyl-1-pentene, 2,3-methyl-2-butene and 4-methylstyrene] has been investigated by combining F-19, H-1-HOESY NMR spectroscopy in (CDCl2)-Cl-2 and a detailed analysis of the Coulomb potential of the cationic fragment through DFT calculations. Two main orientations have been found where the anion locates close to the imidazole ring (NHC-side) and close to the olefin (olefin-side). The NHC-side orientation is always predominant (65-83%) while the exact position of the anion in the olefin-side is finely tuned by the nature of olefin substituents. In all cases, the counterion resides far away from the gold site, the latter carrying only a small fraction of the positive charge. (C) 2010 Elsevier B.V. All rights reserved.

引用

页码：2679 / 2686

页数：8

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