Homoleptic Two-Coordinate Silylamido Complexes of Chromium(I), Manganese(I), and Cobalt(I)

C. Gunnar Werncke; Elizaveta Suturina; Philip C. Bunting; Laure Vendier; Jeffrey R. Long; Mihail Atanasov; Frank Neese; Sylviane Sabo-Etienne; Sébastien Bontemps

doi:10.1002/chem.201503980

Homoleptic Two-Coordinate Silylamido Complexes of Chromium(I), Manganese(I), and Cobalt(I)

C. Gunnar Werncke, Elizaveta Suturina, Philip C. Bunting, Laure Vendier, Jeffrey R. Long, Mihail Atanasov, Frank Neese, Sylviane Sabo-Etienne, Sébastien Bontemps

Department of Chemistry

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

67 Citations (SciVal)

Abstract

Anionic two-coordinate complexes of first-row transition-metal(I) centres are rare molecules that are expected to reveal new magnetic properties and reactivity. Recently, we demonstrated that a N(SiMe₃)₂ ^- ligand set, which is unable to prevent dimerisation or extraneous ligand coordination at the +2 oxidation state of iron, was nonetheless able to stabilise anionic two-coordinate Fe^I complexes even in the presence of a Lewis base. We now report analogous Cr^I and Co^I complexes with exclusively this amido ligand and the isolation of a [Mn^I{N(SiMe₃)₂}₂]₂ ^2- dimer that features a Mn-Mn bond. Additionally, by increasing the steric hindrance of the ligand set, the two-coordinate complex [Mn^I{N(Dipp)(SiMe₃)}₂]^- was isolated (Dipp=2,6-iPr₂-C₆H₃). Characterisation of these compounds by using X-ray crystallography, NMR spectroscopy, and magnetic susceptibility measurements is provided along with ligand-field analysis based on CASSCF/NEVPT2 ab initio calculations.

Original language	English
Pages (from-to)	1668-1674
Number of pages	7
Journal	Chemistry - A European Journal
Volume	22
Issue number	5
Early online date	18 Dec 2015
DOIs	https://doi.org/10.1002/chem.201503980
Publication status	Published - 26 Jan 2016

Funding

C.G.W., S.B. and S.S.E. thank the ANR (programme blanc "IRONHYC" ANR-12), the DFG (WE 5627/1-1 personal grant for C.G.W.) and the CNRS for financial support. Collection and analysis of the magnetic susceptibility data were supported by NSF grant (CHE-1464841) to J.R.L.

Keywords

ab initio calculations
coordination modes
magnetic properties
N ligands
transition metals

ASJC Scopus subject areas

General Chemistry

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10.1002/chem.201503980

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title = "Homoleptic Two-Coordinate Silylamido Complexes of Chromium(I), Manganese(I), and Cobalt(I)",

abstract = "Anionic two-coordinate complexes of first-row transition-metal(I) centres are rare molecules that are expected to reveal new magnetic properties and reactivity. Recently, we demonstrated that a N(SiMe3)2 - ligand set, which is unable to prevent dimerisation or extraneous ligand coordination at the +2 oxidation state of iron, was nonetheless able to stabilise anionic two-coordinate FeI complexes even in the presence of a Lewis base. We now report analogous CrI and CoI complexes with exclusively this amido ligand and the isolation of a [MnI\{N(SiMe3)2\}2]2 2- dimer that features a Mn-Mn bond. Additionally, by increasing the steric hindrance of the ligand set, the two-coordinate complex [MnI\{N(Dipp)(SiMe3)\}2]- was isolated (Dipp=2,6-iPr2-C6H3). Characterisation of these compounds by using X-ray crystallography, NMR spectroscopy, and magnetic susceptibility measurements is provided along with ligand-field analysis based on CASSCF/NEVPT2 ab initio calculations.",

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author = "Werncke, \{C. Gunnar\} and Elizaveta Suturina and Bunting, \{Philip C.\} and Laure Vendier and Long, \{Jeffrey R.\} and Mihail Atanasov and Frank Neese and Sylviane Sabo-Etienne and S{\'e}bastien Bontemps",

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doi = "10.1002/chem.201503980",

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AU - Werncke, C. Gunnar

AU - Suturina, Elizaveta

AU - Bunting, Philip C.

AU - Vendier, Laure

AU - Long, Jeffrey R.

AU - Atanasov, Mihail

AU - Neese, Frank

AU - Sabo-Etienne, Sylviane

AU - Bontemps, Sébastien

PY - 2016/1/26

Y1 - 2016/1/26

N2 - Anionic two-coordinate complexes of first-row transition-metal(I) centres are rare molecules that are expected to reveal new magnetic properties and reactivity. Recently, we demonstrated that a N(SiMe3)2 - ligand set, which is unable to prevent dimerisation or extraneous ligand coordination at the +2 oxidation state of iron, was nonetheless able to stabilise anionic two-coordinate FeI complexes even in the presence of a Lewis base. We now report analogous CrI and CoI complexes with exclusively this amido ligand and the isolation of a [MnI{N(SiMe3)2}2]2 2- dimer that features a Mn-Mn bond. Additionally, by increasing the steric hindrance of the ligand set, the two-coordinate complex [MnI{N(Dipp)(SiMe3)}2]- was isolated (Dipp=2,6-iPr2-C6H3). Characterisation of these compounds by using X-ray crystallography, NMR spectroscopy, and magnetic susceptibility measurements is provided along with ligand-field analysis based on CASSCF/NEVPT2 ab initio calculations.

AB - Anionic two-coordinate complexes of first-row transition-metal(I) centres are rare molecules that are expected to reveal new magnetic properties and reactivity. Recently, we demonstrated that a N(SiMe3)2 - ligand set, which is unable to prevent dimerisation or extraneous ligand coordination at the +2 oxidation state of iron, was nonetheless able to stabilise anionic two-coordinate FeI complexes even in the presence of a Lewis base. We now report analogous CrI and CoI complexes with exclusively this amido ligand and the isolation of a [MnI{N(SiMe3)2}2]2 2- dimer that features a Mn-Mn bond. Additionally, by increasing the steric hindrance of the ligand set, the two-coordinate complex [MnI{N(Dipp)(SiMe3)}2]- was isolated (Dipp=2,6-iPr2-C6H3). Characterisation of these compounds by using X-ray crystallography, NMR spectroscopy, and magnetic susceptibility measurements is provided along with ligand-field analysis based on CASSCF/NEVPT2 ab initio calculations.

KW - ab initio calculations

KW - coordination modes

KW - magnetic properties

KW - N ligands

KW - transition metals

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Homoleptic Two-Coordinate Silylamido Complexes of Chromium(I), Manganese(I), and Cobalt(I)

Abstract

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Keywords

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