The Charge Transfer Approach to Heavier Main-Group Element Radicals in Transition-Metal Complexes

Gengwen Tan; Jing Li; Li Zhang; Chao Chen; Yue Zhao; Xinping Wang; You Song; Yi-Quan Zhang; Matthias Driess

doi:10.1002/anie.201707501

The Charge Transfer Approach to Heavier Main-Group Element Radicals in Transition-Metal Complexes

Angew Chem Int Ed Engl. 2017 Oct 2;56(41):12741-12745. doi: 10.1002/anie.201707501. Epub 2017 Aug 30.

Authors

Gengwen Tan¹, Jing Li¹, Li Zhang¹, Chao Chen¹, Yue Zhao¹, Xinping Wang¹, You Song¹, Yi-Quan Zhang², Matthias Driess³

Affiliations

¹ State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, 210023, China.
² Jiangsu Key Laboratory for NSLSCS, School of Physical Science and Technology, Nanjing Normal University, Nanjing, 210023, China.
³ Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, 10623, Berlin, Germany.

PMID: 28801962
DOI: 10.1002/anie.201707501

Abstract

The Co^II and Fe^II complexes 1Co and 1Fe with a coordinated phosphorus radical were easily obtained through a charge-transfer approach from the M^I precursors LM^I (tol) (M=Co, Fe; L=CH(MeC=NDipp)₂ , Dipp=2,6-iPr₂ C₆ H₃ ) to the diazafluorenylidene-substituted phosphaalkene 1. Structural, magnetic, and computational studies on 1Co and 1Fe indicate a weak antiferromagnetic interaction between the high-spin M^II ion and the phosphorus radical, resulting in a triplet and quartet ground state, respectively. Complexes 1Co and 1Fe are the first examples of phosphorus-radical-coordinated transition-metal complexes synthesized by charge transfer, providing a new approach to access radicals of heavier main-group elements.

Keywords: charge-transfer complexes; cobalt; iron; magnetic properties; phosphorus radicals.

Publication types

Research Support, Non-U.S. Gov't