Electrochemically Controlling Ligand Binding Affinity for Transition Metals via RHLs: The Importance of Electrostatic Effects
作者:Alan M. Allgeier、Caroline S. Slone、Chad A. Mirkin、Louise M. Liable-Sands、Glenn P. A. Yap、Arnold L. Rheingold
DOI:10.1021/ja963008a
日期:1997.1.1
A series of redox-switchable hemilabile ligands (RHLs) has been synthesized that incorporates ferrocene as the redox group and phosphine ether or phosphine thioether moieties as binding groups. These ligands, which complex to Rh(I) and Pd(II), yield electrochemical control over ligand binding affinity for transition metals in complexes of the following type: [M(η4-(η5-C5H4XCH2CH2PR2)2Fe)]y+ (5: M =
已经合成了一系列氧化还原可切换的半稳定配体 (RHL),其中包含二茂铁作为氧化还原基团和膦醚或膦硫醚部分作为结合基团。这些配体与 Rh(I) 和 Pd(II) 复合,在以下类型的配合物中对配体与过渡金属的结合亲和力产生电化学控制:[M(η4-(η5-C5H4XCH2CH2PR2)2Fe)]y+ (5: M = Rh,X = O,R = Ph(苯基),y = 1;6:M = Rh,X = O,R = Cy(环己基),y = 1;9:M = Rh,X = S, R = Ph,y = 1;10:M = Pd,X = O,R = Ph,y = 2;11:M = Pd,X = O,R = Cy,y = 2)。在 11 的情况下,基于配体的氧化将配体与金属的结合常数降低了近十个数量级。5, 9, 10 的晶体结构检查,和 11 以及一系列 RHL 配合物和等电子模型配合物的电化学行为表明,静电效应在这