University of Oulu

Freitag, K., Stennett, C. R., Mansikkamäki, A., Fischer, R. A., & Power, P. P. (2021). Two-Coordinate, Nonlinear Vanadium(II) and Chromium(II) Complexes of the Silylamide Ligand–N(SiMePh2)2: Characterization and Confirmation of Orbitally Quenched Magnetic Moments in Complexes with Sub-d5 Electron Configurations. Inorganic Chemistry, 60(6), 4108–4115. https://doi.org/10.1021/acs.inorgchem.1c00168

Two-coordinate, non-linear vanadium(II) and chromium(II) complexes of the silylamide ligand –N(SiMePh₂)₂ : characterization and confirmation of orbitally quenched magnetic moments in complexes with sub-d⁵ electron configurations

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Author: Freitag, Kerstin1; Stennett, Cary R.2; Mansikkamäki, Akseli3;
Organizations: 1Inorganic and Metalorganic Chemistry, Technical University Munich, D-85748, Garching, Germany
2Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, California 95616, United States
3NMR Research Unit, Faculty of Science, University of Oulu, P.O. Box 3000, Oulu, FIN-90014, Finland
Format: article
Version: accepted version
Access: embargoed
Persistent link: http://urn.fi/urn:nbn:fi-fe202103319155
Language: English
Published: American Chemical Society, 2021
Publish Date: 2022-02-23
Description:

Abstract

The two-coordinate metal amide complexes V{N(SiMePh₂)₂}₂ (1) and Cr{N(SiMe₂Ph)₂}₂ (2) were synthesized by reaction of two equivalents of LiN(SiMePh₂)₂ with VI₂(THF)₄ or CrCl₂(THF)₂ in n-hexane. Their crystal structures showed that they have bent coordination, N-V-N = 137.0(4)°, N-Cr-N = 139.19(5)°, at the metals. The vanadium complex (1) displayed no tendency to isomerize as previously observed for some V(II) amido complexes. Curie fits of SQUID magnetic measurements afforded magnetic moments of 3.36 (1) and 4.68 (2) μB, consistent with high-spin configurations. These values are lower than the spin-only values of 3.88 and 4.90 μB expected for d³ and d⁴ complexes, suggesting a significant unquenched orbital angular momentum contribution to the overall moment, which is lower as a result of the positive spin-orbit coupling constants.

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Series: Inorganic chemistry
ISSN: 0020-1669
ISSN-E: 1520-510X
ISSN-L: 0020-1669
Volume: 60
Issue: 6
Pages: 4108 - 4115
DOI: 10.1021/acs.inorgchem.1c00168
OADOI: https://oadoi.org/10.1021/acs.inorgchem.1c00168
Type of Publication: A1 Journal article – refereed
Field of Science: 114 Physical sciences
116 Chemical sciences
Subjects:
Funding: This research was funded by the US National Science Foundation, Grant No. CHE-1565501. The dissertation project of K.F. was funded by the German Chemical Industry Fund (https://www.vci.de/fonds) and further supported by the RUB Research School (http://www.research.school.rub.de). C.R.S. and P.P.P. wish to acknowledge the US National Science Foundation (CHE-1565501) and A.M. acknowledges the Academy of Finland (grant no. 332294) and the University of Oulu (Kvantum Institute) for support of this work.
Academy of Finland Grant Number: 332294
Detailed Information: 332294 (Academy of Finland Funding decision)
Dataset Reference: The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.1c00168.
  https://pubs.acs.org/doi/10.1021/acs.inorgchem.1c00168
Copyright information: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.inorgchem.1c00168.