State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, 210023, China.
Jiangsu Key Laboratory for NSLSCS, School of Physical Science and Technology, Nanjing Normal University, Nanjing, 210023, China.
Angew Chem Int Ed Engl. 2017 Oct 2;56(41):12741-12745. doi: 10.1002/anie.201707501. Epub 2017 Aug 30.
The Co and Fe complexes 1Co and 1Fe with a coordinated phosphorus radical were easily obtained through a charge-transfer approach from the M precursors LM (tol) (M=Co, Fe; L=CH(MeC=NDipp) , Dipp=2,6-iPr C H ) 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 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.
通过从 M 前体 LM(tol)（M=Co，Fe；L=CH(MeC=NDipp)，Dipp=2,6-iPr 2 C 6 H 3 ）到取代的二氮杂芴基亚磷烯 1 的电荷转移，容易得到 Co 和 Fe 配合物 1Co 和 1Fe，其中磷自由基配位。对 1Co 和 1Fe 的结构、磁性和计算研究表明，高自旋 M 离子和磷自由基之间存在弱反铁磁相互作用，分别导致三重态和四重态基态。配合物 1Co 和 1Fe 是通过电荷转移合成的磷自由基配位过渡金属配合物的首例实例，为获得较重主族元素的自由基提供了一种新方法。
