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

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

doi:10.1002/anie.202104320

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

Journal Article · Mon Apr 19 00:00:00 EDT 2021 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202104320· OSTI ID:1784726

^[1]; Semproni, Scott P. ^[2]; Zhong, Hongyu ^[2]; ^[2]

Princeton Univ., NJ (United States); Princeton University
Princeton Univ., NJ (United States)

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. Here, 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.

View Accepted Manuscript (DOE)

Research Organization:: Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0006498

OSTI ID:: 1784726

Alternate ID(s):: OSTI ID: 1784436

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 26 Vol. 60; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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CCDC 2072859: Experimental Crystal Structure Determination Yoonsu, Park,; P., Semproni, Scott; Hongyu, Zhong, https://doi.org/10.5517/ccdc.csd.cc27kzf7 The current record is supplemented by this dataset	dataset	January 2021
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CCDC 2072861: Experimental Crystal Structure Determination Yoonsu, Park,; P., Semproni, Scott; Hongyu, Zhong, https://doi.org/10.5517/ccdc.csd.cc27kzh9 The current record is supplemented by this dataset	dataset	January 2021

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

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