Synthesis, Electronic Structure, and Reactivity of a Planar Four-Coordinate, Cobalt–Imido Complex

Yoonsu Park, Scott P. Semproni, Hongyu Zhong, Paul J. Chirik

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

A four-coordinate cobalt–imido complex, (tBumPNP)Co=NMes (tBumPNP=modified PNP pincer ligand) has been synthesized from addition of 2,4,6-trimethylphenylazide (Mes–N3) 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.

Original languageEnglish (US)
Pages (from-to)14376-14380
Number of pages5
JournalAngewandte Chemie - International Edition
Volume60
Issue number26
DOIs
StatePublished - Jun 21 2021

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Keywords

  • CASSCF
  • cobalt
  • electronic structure
  • imido
  • nitrene transfer

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