Complexes of Dichlorogermylene with Phosphine/Sulfoxide-Supported Carbone as Ligand.

Ugo Authesserre,Nathalie Saffon-Merceron,Eddy Maerten,Sophie Hameury,Aymeric Dajnak,David Madec,Antoine Baceiredo

doi:10.3390/molecules26072005

Abstract

Due to their remarkable electronic features, recent years have witnessed the emergence of carbones L2C, which consist in two donating L ligands coordinating a central carbon atom bearing two lone pairs. In this context, the phosphine/sulfoxide-supported carbone 4 exhibits a strong nucleophilic character, and here, we describe its ability to coordinate dichlorogermylene. Two original stable coordination complexes were obtained and fully characterized in solution and in the solid state by NMR spectroscopy and X-ray diffraction analysis, respectively. At 60 °C, in the presence of 4, the Ge(II)-complex 5 undergoes a slow isomerization that transforms the bis-ylide ligand into an yldiide.

Highlights

The rapid development of homogeneous catalysis in the last decades is highly related to the intensive research that was accomplished toward ligand design
Due to their remarkable electronic features, recent years have witnessed the emergence of carbones L2C, which consist in two donating L ligands coordinating a central carbon atom bearing two lone pairs
The phosphine/sulfoxide-supported carbone 4 exhibits a strong nucleophilic character, and here, we describe its ability to coordinate dichlorogermylene

Summary

Introduction

The rapid development of homogeneous catalysis in the last decades is highly related to the intensive research that was accomplished toward ligand design Due to their lone pair(s) and their related nucleophilic character, oxygen-, nitrogen-, sulfur- and phosphoruscontaining ligands have been dominating in the field for several decades [1]. Even though carbodiphosphoranes (II, L, L = PPh3) were discovered in the 1960s by Ramirez [8], these species were at first regarded as two cumulated phosphorus ylide functions on a central carbon atom It was only in 2006, after the theoretical investigations by Frenking et al [9,10,11,12], that these molecules were considered as a carbon atom in the zerooxidation state stabilized by two L-phosphine ligands, in agreement with the description initially used by Kaska in 1973 [13]. Owing to the existence of two lone pairs, they are strong σ- and π-donors (two- or four-electron donating ability); they have been used as original ligands for the preparation of organometallic complexes with interesting applications in catalysis [24,25,26,27,28,29]

Methods

Results

Conclusion