Centre for Catalysis Research and Innovation and Department of Chemistry, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada.
Dalton Trans. 2012 Apr 28;41(16):4765-71. doi: 10.1039/c2dt12112c. Epub 2012 Feb 3.
The bis(imino)pyridine scaffold provides support for the synthesis and characterization of unique Ag(I) pincer complexes [{ArN=CPh}(2)(NPh)]Ag(+)(OTf)(-) (Ar = 2,5-(t)Bu(2)C(6)H(3)3; 2,6-(i)Pr(2)C(6)H(3) 4). The bonding interactions between the cation-anion and between the bis(imino)pyridine ligand and the Ag centre are presented. Coordination of pyridine, toluene, 2-butyne and cyclooctene to the Ag centre led to the isolation and crystallographic characterization of labile transient adduct species. Bonding analysis of the adducts revealed conventional ligand-Ag coordination and important unconventional electron donation from the ligand to a π*-orbital of the bis(imino)pyridine group.
双（亚胺基）吡啶支架为独特的 Ag(I) 夹式配合物 [{ArN=CPh}(2)(NPh)]Ag(+)(OTf)(-)（Ar = 2,5-(t)Bu(2)C(6)H(3)3；2,6-(i)Pr(2)C(6)H(3) 4）的合成和特性研究提供了支持。本文介绍了阳离子-阴离子之间以及双（亚胺基）吡啶配体与 Ag 中心之间的键合相互作用。吡啶、甲苯、2-丁炔和环辛烯与 Ag 中心的配位导致了不稳定瞬态加合物的分离和晶体学表征。加合物的键合分析表明存在常规的配体-Ag 配位，以及来自配体到双（亚胺基）吡啶基团的π*-轨道的重要非常规电子供体。
