Heteroleptic Square Planar Cobalt(I/II) Complexes

Yafei Gao; Wei Tsung Lee; Veronica Carta; Chun Hsing Chen; Joshua Telser; Jeremy M. Smith

doi:10.1002/ejic.202200675

Heteroleptic Square Planar Cobalt(I/II) Complexes

Yafei Gao, Wei Tsung Lee, Veronica Carta, Chun Hsing Chen, Joshua Telser, Jeremy M. Smith

Department of Chemistry

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

3 Scopus citations

Abstract

Reduction of the cobalt(II) chloride complex, Ph₂B(^tBuIm)₂Co(THF)Cl (1) in the presence of ^tBuN≡C affords the diamagnetic, square planar cobalt(I) complex Ph₂B(^tBuIm)₂Co(C≡N^tBu)₂ (2). This is a rare example of a 16-electron cobalt(I) complex that is structurally related to square planar noble metal complexes. Accordingly, the electronic structure of 2, as calculated by DFT, reveals that the HOMO is largely d_z² in character. Complex 2 is readily oxidized to its cobalt(II) congener [Ph₂B(^tBuIm)₂Co(C=N^tBu)₂]BPh₄ (3-BPh₄), whose EPR spectral parameters are characteristic of low-spin d⁷ with an unpaired electron in an orbital of d_z² parentage. This is also consistent with the results of DFT calculations. Despite its 16-electron configuration and the d_z² parentage of the HOMO, the only tractable reactions of 2 involve one electron oxidation to afford 3.

Original language	English
Article number	e202200675
Journal	European Journal of Inorganic Chemistry
Volume	26
Issue number	8
DOIs	https://doi.org/10.1002/ejic.202200675
State	Published - 9 Mar 2023

Keywords

Carbene ligands
Cobalt
Electronic structure
Isocyanide ligands
Structure elucidation

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title = "Heteroleptic Square Planar Cobalt(I/II) Complexes",

abstract = "Reduction of the cobalt(II) chloride complex, Ph2B(tBuIm)2Co(THF)Cl (1) in the presence of tBuN≡C affords the diamagnetic, square planar cobalt(I) complex Ph2B(tBuIm)2Co(C≡NtBu)2 (2). This is a rare example of a 16-electron cobalt(I) complex that is structurally related to square planar noble metal complexes. Accordingly, the electronic structure of 2, as calculated by DFT, reveals that the HOMO is largely dz2 in character. Complex 2 is readily oxidized to its cobalt(II) congener [Ph2B(tBuIm)2Co(C=NtBu)2]BPh4 (3-BPh4), whose EPR spectral parameters are characteristic of low-spin d7 with an unpaired electron in an orbital of dz2 parentage. This is also consistent with the results of DFT calculations. Despite its 16-electron configuration and the dz2 parentage of the HOMO, the only tractable reactions of 2 involve one electron oxidation to afford 3.",

keywords = "Carbene ligands, Cobalt, Electronic structure, Isocyanide ligands, Structure elucidation",

author = "Yafei Gao and Lee, {Wei Tsung} and Veronica Carta and Chen, {Chun Hsing} and Joshua Telser and Smith, {Jeremy M.}",

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T1 - Heteroleptic Square Planar Cobalt(I/II) Complexes

AU - Gao, Yafei

AU - Lee, Wei Tsung

AU - Carta, Veronica

AU - Chen, Chun Hsing

AU - Telser, Joshua

AU - Smith, Jeremy M.

PY - 2023/3/9

Y1 - 2023/3/9

N2 - Reduction of the cobalt(II) chloride complex, Ph2B(tBuIm)2Co(THF)Cl (1) in the presence of tBuN≡C affords the diamagnetic, square planar cobalt(I) complex Ph2B(tBuIm)2Co(C≡NtBu)2 (2). This is a rare example of a 16-electron cobalt(I) complex that is structurally related to square planar noble metal complexes. Accordingly, the electronic structure of 2, as calculated by DFT, reveals that the HOMO is largely dz2 in character. Complex 2 is readily oxidized to its cobalt(II) congener [Ph2B(tBuIm)2Co(C=NtBu)2]BPh4 (3-BPh4), whose EPR spectral parameters are characteristic of low-spin d7 with an unpaired electron in an orbital of dz2 parentage. This is also consistent with the results of DFT calculations. Despite its 16-electron configuration and the dz2 parentage of the HOMO, the only tractable reactions of 2 involve one electron oxidation to afford 3.

AB - Reduction of the cobalt(II) chloride complex, Ph2B(tBuIm)2Co(THF)Cl (1) in the presence of tBuN≡C affords the diamagnetic, square planar cobalt(I) complex Ph2B(tBuIm)2Co(C≡NtBu)2 (2). This is a rare example of a 16-electron cobalt(I) complex that is structurally related to square planar noble metal complexes. Accordingly, the electronic structure of 2, as calculated by DFT, reveals that the HOMO is largely dz2 in character. Complex 2 is readily oxidized to its cobalt(II) congener [Ph2B(tBuIm)2Co(C=NtBu)2]BPh4 (3-BPh4), whose EPR spectral parameters are characteristic of low-spin d7 with an unpaired electron in an orbital of dz2 parentage. This is also consistent with the results of DFT calculations. Despite its 16-electron configuration and the dz2 parentage of the HOMO, the only tractable reactions of 2 involve one electron oxidation to afford 3.

KW - Carbene ligands

KW - Cobalt

KW - Electronic structure

KW - Isocyanide ligands

KW - Structure elucidation

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DO - 10.1002/ejic.202200675

M3 - 期刊論文

AN - SCOPUS:85146076817

SN - 1434-1948

VL - 26

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 8

M1 - e202200675

ER -

Heteroleptic Square Planar Cobalt(I/II) Complexes

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Keywords

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