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

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

doi:10.1002/anie.202104320

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

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

Chemistry

Princeton University

Research output: Contribution to journal › Article › peer-review

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 language	American English
Pages (from-to)	14376-14380
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	26
DOIs	https://doi.org/10.1002/anie.202104320
State	Published - Jun 21 2021

ASJC Scopus subject areas

General Chemistry
Catalysis

Keywords

CASSCF
cobalt
electronic structure
imido
nitrene transfer

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10.1002/anie.202104320

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

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) {\AA}. 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.",

keywords = "CASSCF, cobalt, electronic structure, imido, nitrene transfer",

author = "Yoonsu Park and Semproni, \{Scott P.\} and Hongyu Zhong and Chirik, \{Paul J.\}",

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year = "2021",

month = jun,

day = "21",

doi = "10.1002/anie.202104320",

language = "American English",

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TY - JOUR

T1 - Synthesis, Electronic Structure, and Reactivity of a Planar Four-Coordinate, Cobalt–Imido Complex

AU - Park, Yoonsu

AU - Semproni, Scott P.

AU - Zhong, Hongyu

AU - Chirik, Paul J.

PY - 2021/6/21

Y1 - 2021/6/21

N2 - 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.

AB - 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.

KW - CASSCF

KW - cobalt

KW - electronic structure

KW - imido

KW - nitrene transfer

UR - https://www.scopus.com/pages/publications/85106246689

UR - https://www.scopus.com/pages/publications/85106246689#tab=citedBy

U2 - 10.1002/anie.202104320

DO - 10.1002/anie.202104320

M3 - Article

C2 - 33876539

SN - 1433-7851

VL - 60

SP - 14376

EP - 14380

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 26

ER -

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

Abstract

ASJC Scopus subject areas

Keywords

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