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Oxidative P−P Bond Addition to Cobalt(−I): Formation of a Low‐Spin Cobalt(III) Phosphanido Complex
Author(s) -
Coburger Peter,
Demeshko Serhiy,
Rödl Christian,
HeyHawkins Evamarie,
Wolf Robert
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201709140
Subject(s) - cobalt , homoleptic , chemistry , ground state , crystallography , ligand (biochemistry) , singlet state , oxidative addition , bond length , spin states , inorganic chemistry , crystal structure , metal , excited state , catalysis , organic chemistry , atomic physics , physics , biochemistry , receptor
The first homoleptic cobalt phosphanido complex [K(thf) 4 ][Co{1,2‐(P t Bu 2 ) 2 C 2 B 10 H 12 } 2 ] ( 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) 0.2 ][Co(η 4 ‐cod) 2 )] (cod=1,5‐cycloctadiene). Compound 1 is a rare distorted tetrahedral 3d 6 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 8 ]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.