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投稿者: Yuma Morimoto

Article

Molecular and Electronic Structures of the Members of the Electron Transfer Series [Mn(bpy)3]n (n = 2+, 1+, 0, 1−) and [Mn(tpy)2]m (m = 4+, 3+, 2+, 1+, 0). An Experimental and Density Functional Theory Study

Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34−36, D-45470 Mülheim an der Ruhr,Germany
Inorg. Chem., Article ASAP
DOI: 10.1021/ic4029854
Publication Date (Web): January 27, 2014
Copyright © 2014 American Chemical Society

Synopsis

The complexes [MnII(Mebpy•)2(Mebpy0)]0, [Li(THF)4][MnII(bpy•)3], and [MnII(tpy•)2]0 have been characterized using a combination of X-ray crystallography and spectroscopy. These studies, augmented by DFT calculations for the series [Mn(bpy)3]n (n = 2+, 1+, 0, 1−) and [Mn(tpy)2]m (m = 2+, 1+, 0), allowed definitive electronic structure assignment for these complexes and the others members of the aforementioned electron transfer series. All contain high-spin MnII and possess localized electronic structures.
Inorganic Chemicals and Reactions

Abstract

Abstract Image
The members of the electron transfer series [Mn(bpy)3]n (n = 2+, 1+, 0, 1−) and [Mn(tpy)2]m(m = 2+, 1+, 0) have been investigated using a combination of magnetochemistry, electrochemistry, and UV–vis–NIR spectroscopy; and X-ray crystal structures of [MnII(Mebpy•)2(Mebpy0)]0, [Li(THF)4][MnII(bpy•)3], and [MnII(tpy•)2]0 have been obtained (bpy = 2,2′-bipyridine; Mebpy = 4,4′-dimethyl-2,2′-bipyridine; tpy = 2,2′:6,2″-terpyridine; THF = tetrahydrofuran). It is the first time that the latter complex has been isolated and characterized. Through these studies, the electronic structures of each member of both series of complexes have been elucidated, and their molecular and electronic structures further corroborated by broken symmetry (BS) density functional theoretical (DFT) calculations. It is shown that all one-electron reductions that comprise the aforementioned redox series are ligand-based. Hence, all species contain a central high-spin MnII ion (SMn = 5/2). In contrast, the analogous series of TcII and ReII complexes possess low-spin electron configurations.
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