Leipzig University, Faculty of Chemistry and Mineralogy, Institute of Inorganic Chemistry, Johannisallee 29, 04103, Leipzig, Germany.
Göttingen University, Faculty of Chemistry, Tammanstrasse 4, 37077, Göttingen, Germany.
Angew Chem Int Ed Engl. 2017 Dec 11;56(50):15871-15875. doi: 10.1002/anie.201709140. Epub 2017 Nov 15.
The first homoleptic cobalt phosphanido complex [K(thf) ][Co{1,2-(PtBu ) C B H } ] (1) was prepared by an unprecedented oxidative P-P bond addition of an ortho-carborane-substituted 1,2-diphosphetane to cobalt(-I) in [K(thf) ][Co(η -cod) )] (cod=1,5-cycloctadiene). Compound 1 is a rare distorted tetrahedral 3d complex with a low-spin ground state configuration. Magnetic measurements revealed that the complex is diamagnetic between 2 to 270 K in the solid state and at 298 K in [D ]THF solution. Based on DFT calculations, the unusual singlet ground state is caused by the strong σ-donor and moderate π-donor properties of the bis(phosphanido) ligand.
首例同核钴膦配合物[K(thf) ][Co{1,2-(PtBu ) C B H } ]（1）通过前所未有的邻位碳硼取代的 1,2-二膦烷对[K(thf) ][Co(η -cod) )]（cod=1,5-环辛二烯）中钴（-I）的氧化 P-P 键加成制备得到。化合物 1 是一种罕见的扭曲四面体 3d 配合物，具有低自旋基态构型。磁性测量表明，该配合物在固态下在 2 至 270 K 以及在 [D ]THF 溶液中在 298 K 时为抗磁性。基于 DFT 计算，这种不寻常的单重态基态是由双（膦基）配体的强σ给体和中等π给体性质引起的。
