Coordination-Induced Spin-State Change in Manganese(V) Complexes: The Electronic Structure of Manganese(V) Nitrides

Kropp H, Scheurer A, Heinemann FW, Bendix J, Meyer K (2015)

Publication Language: English

Publication Type: Journal article, Report

Publication year: 2015

Journal

Inorganic Chemistry American Chemical Society

Publisher: American Chemical Society

Book Volume: 54

Pages Range: 3562–3572

Journal Issue: 7

URI: http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.5b00112

DOI: 10.1021/acs.inorgchem.5b00112

Abstract

This work illustrates that manganese(V) nitrido complexes are able to undergo a coordination-induced spin-state change by altering the ligand field from trigonal to tetragonal symmetry. For the reversible coordination of acetonitrile to trigonal [(TIMENxyl)Mn(N)]2+ (1; high-spin S = 1; with TIMENxyl = tris[2-(3-xylylimidazol-2-ylidene)ethyl]-amine), a temperature-dependent coordination-induced spin-state switch is established. Starting from the manganese(V) nitrido complex 1, the synthesis and characterization of a series of octahedral, low-spin (S = 0) manganese(V) nitrido complexes of the type [(TIMENxyl)Mn(N)(L)]n+ (L = MeCN (2), tBuNC (3), CN– (4), NCS– (5), F– (6), μ-{Ag(CN)2}− (7), with n = 1, 2) is described. These represent the first examples of d2 transition metal complexes showing a coordination-induced spin-state change. Spectroscopic, as well as ligand-field theory and density functional theory studies suggest a transition from a 2 + 2 + 1 orbital splitting in the trigonal case to a 1 + 2 + 1 + 1 splitting in tetragonal symmetry as the origin of the coordination-induced spin-state change.

Authors with CRIS profile

Henning Kropp Lehrstuhl für Anorganische und Allgemeine Chemie Andreas Scheurer Lehrstuhl für Anorganische und Allgemeine Chemie Frank Wilhelm Heinemann Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

University of Copenhagen DK Denmark (DK)

How to cite

APA:

Kropp, H., Scheurer, A., Heinemann, F.W., Bendix, J., & Meyer, K. (2015). Coordination-Induced Spin-State Change in Manganese(V) Complexes: The Electronic Structure of Manganese(V) Nitrides. Inorganic Chemistry, 54(7), 3562–3572. https://dx.doi.org/10.1021/acs.inorgchem.5b00112

MLA:

Kropp, Henning, et al. "Coordination-Induced Spin-State Change in Manganese(V) Complexes: The Electronic Structure of Manganese(V) Nitrides." Inorganic Chemistry 54.7 (2015): 3562–3572.

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