Mononuclear Four-Coordinate Bis-Fluoride Bis-NHC Complexes of Chromium(II), Iron(II), and Cobalt(II)

Carlos M. Acosta; Dmitry S. Belov; Andy H. Lamur; Christi Anna L. Brantley; Xavier Solans-Monfort; Kelly L. Rue; George Christou; Konstantin V. Bukhryakov

doi:10.1021/acs.inorgchem.3c02442

Mononuclear Four-Coordinate Bis-Fluoride Bis-NHC Complexes of Chromium(II), Iron(II), and Cobalt(II)

Carlos M. Acosta, Dmitry S. Belov, Andy H. Lamur, Christi Anna L. Brantley, Xavier Solans-Monfort, Kelly L. Rue, George Christou, Konstantin V. Bukhryakov

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

Abstract

The reaction between silylamido complexes of Cr(II), Fe(II), and Co(II) and IMes·2HF salt in the presence of IMes (IMes = 1,3-dimesitylimidazol-2-ylidene) led to isolation of Cr(IMes)₂F₂ (2-Cr), Fe(IMes)₂F₂ (2-Fe), and Co(IMes)₂F₂ (2-Co). X-ray structural studies revealed that 2-Cr adopts square planar geometry, while 2-Fe and 2-Co have distorted tetrahedral geometry. Magnetic susceptibility studies of 2-Cr, 2-Fe, and 2-Co were consistent with high-spin complexes, S = 2 for 2-Cr/2-Fe and S = 3/2 for 2-Co. We demonstrated that fluoride can be successfully exchanged for cyanide and azide using trimethylsilyl cyanide and trimethylsilyl azide (3-Fe and 4-Fe). DFT studies suggest that the preference of 2-Cr to adopt square planar geometry over tetrahedral is due to its d⁴ metal center, where four electrons fill the lower-lying d-orbitals.

Original language	English
Pages (from-to)	18108-18115
Number of pages	8
Journal	Inorganic Chemistry
Volume	62
Issue number	44
DOIs	https://doi.org/10.1021/acs.inorgchem.3c02442
State	Published - Nov 6 2023
Externally published	Yes

Funding

This work was supported by NSF grant CHE-2212944. The work at the University of Florida was supported by NSF grant CHE-1900321. The work at the Universitat Autònoma de Barcelona was supported by the Spanish MICINN through the PID2020-112715GB-I00 project. K.L.R. was supported by the U.S. Nuclear Regulatory Commission (NRC) fellowship grant no. 31310018M0012 awarded to FIU. We are grateful to Indranil Chakraborty (FIU) and Khalil Abboud (UF) for X-ray studies.

Funders	Funder number
Indranil Chakraborty
Khalil Abboud
National Science Foundation	CHE-1900321, CHE-2212944
U.S. Nuclear Regulatory Commission
Florida International University
University of Florida
National Research Council	31310018M0012
Ministerio de Ciencia e Innovación	PID2020-112715GB-I00

Access to Document

10.1021/acs.inorgchem.3c02442

Cite this

@article{8ff9e94917324a32a81a4f72a42d52e6,

title = "Mononuclear Four-Coordinate Bis-Fluoride Bis-NHC Complexes of Chromium(II), Iron(II), and Cobalt(II)",

abstract = "The reaction between silylamido complexes of Cr(II), Fe(II), and Co(II) and IMes·2HF salt in the presence of IMes (IMes = 1,3-dimesitylimidazol-2-ylidene) led to isolation of Cr(IMes)2F2 (2-Cr), Fe(IMes)2F2 (2-Fe), and Co(IMes)2F2 (2-Co). X-ray structural studies revealed that 2-Cr adopts square planar geometry, while 2-Fe and 2-Co have distorted tetrahedral geometry. Magnetic susceptibility studies of 2-Cr, 2-Fe, and 2-Co were consistent with high-spin complexes, S = 2 for 2-Cr/2-Fe and S = 3/2 for 2-Co. We demonstrated that fluoride can be successfully exchanged for cyanide and azide using trimethylsilyl cyanide and trimethylsilyl azide (3-Fe and 4-Fe). DFT studies suggest that the preference of 2-Cr to adopt square planar geometry over tetrahedral is due to its d4 metal center, where four electrons fill the lower-lying d-orbitals.",

author = "Acosta, {Carlos M.} and Belov, {Dmitry S.} and Lamur, {Andy H.} and Brantley, {Christi Anna L.} and Xavier Solans-Monfort and Rue, {Kelly L.} and George Christou and Bukhryakov, {Konstantin V.}",

note = "Publisher Copyright: {\textcopyright} 2023 American Chemical Society.",

year = "2023",

month = nov,

day = "6",

doi = "10.1021/acs.inorgchem.3c02442",

language = "English",

volume = "62",

pages = "18108--18115",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "44",

}

TY - JOUR

T1 - Mononuclear Four-Coordinate Bis-Fluoride Bis-NHC Complexes of Chromium(II), Iron(II), and Cobalt(II)

AU - Acosta, Carlos M.

AU - Belov, Dmitry S.

AU - Lamur, Andy H.

AU - Brantley, Christi Anna L.

AU - Solans-Monfort, Xavier

AU - Rue, Kelly L.

AU - Christou, George

AU - Bukhryakov, Konstantin V.

PY - 2023/11/6

Y1 - 2023/11/6

N2 - The reaction between silylamido complexes of Cr(II), Fe(II), and Co(II) and IMes·2HF salt in the presence of IMes (IMes = 1,3-dimesitylimidazol-2-ylidene) led to isolation of Cr(IMes)2F2 (2-Cr), Fe(IMes)2F2 (2-Fe), and Co(IMes)2F2 (2-Co). X-ray structural studies revealed that 2-Cr adopts square planar geometry, while 2-Fe and 2-Co have distorted tetrahedral geometry. Magnetic susceptibility studies of 2-Cr, 2-Fe, and 2-Co were consistent with high-spin complexes, S = 2 for 2-Cr/2-Fe and S = 3/2 for 2-Co. We demonstrated that fluoride can be successfully exchanged for cyanide and azide using trimethylsilyl cyanide and trimethylsilyl azide (3-Fe and 4-Fe). DFT studies suggest that the preference of 2-Cr to adopt square planar geometry over tetrahedral is due to its d4 metal center, where four electrons fill the lower-lying d-orbitals.

AB - The reaction between silylamido complexes of Cr(II), Fe(II), and Co(II) and IMes·2HF salt in the presence of IMes (IMes = 1,3-dimesitylimidazol-2-ylidene) led to isolation of Cr(IMes)2F2 (2-Cr), Fe(IMes)2F2 (2-Fe), and Co(IMes)2F2 (2-Co). X-ray structural studies revealed that 2-Cr adopts square planar geometry, while 2-Fe and 2-Co have distorted tetrahedral geometry. Magnetic susceptibility studies of 2-Cr, 2-Fe, and 2-Co were consistent with high-spin complexes, S = 2 for 2-Cr/2-Fe and S = 3/2 for 2-Co. We demonstrated that fluoride can be successfully exchanged for cyanide and azide using trimethylsilyl cyanide and trimethylsilyl azide (3-Fe and 4-Fe). DFT studies suggest that the preference of 2-Cr to adopt square planar geometry over tetrahedral is due to its d4 metal center, where four electrons fill the lower-lying d-orbitals.

UR - http://www.scopus.com/inward/record.url?scp=85176502993&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.3c02442

DO - 10.1021/acs.inorgchem.3c02442

M3 - Article

C2 - 37876243

AN - SCOPUS:85176502993

SN - 0020-1669

VL - 62

SP - 18108

EP - 18115

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 44

ER -

Mononuclear Four-Coordinate Bis-Fluoride Bis-NHC Complexes of Chromium(II), Iron(II), and Cobalt(II)

Abstract

Funding

Access to Document

Other files and links

Fingerprint

Cite this