Reactive Heterobimetallic Complex Combining Divalent Ytterbium and Dimethyl Nickel Fragments.

Wang Wang,Cordier Cordier,Moutet Moutet,Tricoire Tricoire,Nocton Nocton

doi:10.3390/inorganics7050058

Abstract

This article presented the synthesis and characterization of original heterobimetallic species combining a divalent lanthanide fragment and a divalent nickel center bridged by the bipyrimidine ligand, a redox-active ligand. X-ray crystal structures were obtained for the Ni monomer (bipym)NiMe2, 1, as well as the heterobimetallic dimer compounds, Cp*2Yb(bipym)NiMe2, 2, along with 1H solution NMR, solid-state magnetic data, and DFT calculations only for 1. The reactivity with CO was investigated on both compounds and the stoichiometric acetone formation is discussed based on kinetic and mechanistic studies. The key role of the lanthanide fragment was demonstrated by the relatively slow CO migratory insertion step, which indicated the stability of the intermediate.

Highlights

Heterometallic complexes are important objects of study because both metallic fragments have a role to play in the chemical reaction and/or properties of interest [1,2,3]
We successfully synthesized an original molecule with full characterizations containing reductive divalent lanthanide and reactive NiMe2 fragments with a redox-active bridging ligand
It was shown that due to the electron transfer, strong spin density was on the N-heteroatom ligand to the reactive metal center

Summary

Introduction

Heterometallic complexes are important objects of study because both metallic fragments have a role to play in the chemical reaction and/or properties of interest [1,2,3]. The role of one fragment is purely structural and only facilitates the reaction at the other metal center, while in most cases, both fragments have a role and either participate in the fate of the chemical reaction or complete it [8] This particular case was extensively studied in terms of the tandem-reaction catalysts, where, for example, one metal is the source of one reaction, the other of a second one, and the substrate undergoes two chemical transformations in one pot [9,10,11,12]. The recent interest in photochemically active bimetallic complexes is witness to these developments [14,15]

Methods

Results

Conclusion