期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 60, 期 26, 页码 14376-14380出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202104320
关键词
CASSCF; cobalt; electronic structure; imido; nitrene transfer
资金
- U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Catalysis Science program [DE-SC0006498]
- Andlinger Center for Energy and the Environment (Princeton University)
A new four-coordinate cobalt-imido complex was synthesized, exhibiting unique magnetic and thermal properties. This research provides insights into the stability and selectivity of the product through transition state analysis and DFT calculations.
A four-coordinate cobalt-imido complex, ((tBu)mPNP)Co=NMes ((tBu)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) angstrom. 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.
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