Diferrocenylmercury-Bridged Diphosphine: A Chiral, Ambiphilic, and Redox-Active Bidentate Ligand

被引：10

作者：

Kuate, Alain C. Tagne ^{[1
,2
]}

Lalancette, Roger A. ^{[1
]}

Bannenberg, Thomas ^{[3
]}

Jaekle, Frieder ^{[1
]}

机构：

[1] Rutgers Univ Newark, Dept Chem, 73 Warren St, Newark, NJ 07102 USA

[2] Univ Dschang, Fac Sci, Dept Chem, POB 67, Dschang, Cameroon

[3] Tech Univ Carolo Wilhelmina Braunschweig, Inst Anorgan & Analyt Chem, Hagenring 30, D-38106 Braunschweig, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2018年 / 57卷 / 22期

基金：

美国国家科学基金会;

关键词：

ambiphilic ligands; ferrocene; mercury; phosphines; planar chirality; DER-WAALS RADII; LEWIS PAIRS; CRYSTAL-STRUCTURE; MAIN-GROUP; HG-II; COMPLEXES; BORANE; METAL; CHEMISTRY; ACID;

D O I：

10.1002/anie.201803086

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A diphosphine chelate ligand with a wide and flexible bite angle, a unique stereochemical environment, and redox-active and ambiphilic character is reported. Initially generated as its HgCl2 complex by reaction of 1,2-fc(PPh2)-(SnMe3) (fc = ferrocenediyl) with HgCl2 in acetone, treatment with [n-Bu4N]CN readily liberates the free chiral bidentate ligand. An intermolecular ClHg-Cl-Hgfc(2) (2.9929(13) angstrom) action that is unprecedented in ambiphilic ligand chemisn in the solid structure of Hg(fcPPh(2))(2)center dot HgCl2 where the bridging mercury atom acts as a sigma-acceptor. Furthermore, a bis-[Rh(COD)Cl] complex is introduced, which displays relatively short Rh center dot center dot center dot Hg contacts of 3.4765(5) and 3.4013(1) angstrom. Wiberg, indices of 0.12 are determined for these Rh center dot center dot center dot Hg interactions and an AIM analysis reveals bond paths with an electron density rho(r) of 1.2 x 10(-2) and 1.4 x 10(-2) e/a(0)(3) at the bond critical points.

引用

页码：6552 / 6557

页数：6

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