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Synthesis, Electronic Structure, and Reactivity of a Planar Four‐Coordinate, Cobalt–Imido Complex
Author(s) -
Park Yoonsu,
Semproni Scott P.,
Zhong Hongyu,
Chirik Paul J.
Publication year - 2021
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.202104320
Subject(s) - cobalt , chemistry , crystallography , reactivity (psychology) , ligand (biochemistry) , bond length , imide , geometry , pincer movement , selectivity , molecular geometry , thermal decomposition , crystal structure , molecule , polymer chemistry , inorganic chemistry , organic chemistry , catalysis , mathematics , medicine , biochemistry , alternative medicine , receptor , pathology
Abstract A four‐coordinate cobalt–imido complex, ( t Bu mPNP)Co=NMes ( t Bu mPNP=modified PNP pincer ligand) has been synthesized from addition of 2,4,6‐trimethylphenylazide (Mes–N 3 ) to the corresponding dinitrogen complex. The solid‐state structure determined by X‐ray diffraction established a rare, idealized planar geometry with a Co=N bond distance of 1.716(2) Å. Magnetic measurements revealed an S =1 ground state with CAS‐SCF calculations supporting radical character on the imide nitrogen. Thermolysis of the cobalt–imido compound induced selective insertion of the imido group into a Co−P bond and yielded a three‐coordinate cobalt complex with a distorted T‐shaped geometry. Transition state analysis conducted with DFT calculations established the thermodynamic stability of the P–N coupled product and provided insight into the exclusive selectivity.