England, Jason and Wieghardt, K. (2013) 2,2'-bipyridine compounds of group 14 elements: A density functional theory study. Inorganic Chemistry, 52 (17). pp. 10067-10079. ISSN 0020-1669
Full content URL: https://doi.org/10.1021/ic401375a
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Item Type: | Article |
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Item Status: | Live Archive |
Abstract
The molecular and electronic structures of the 2,2′-bipyridine containing series of group 14 compounds (a) [MF4(bpy)]0; (b) [MCl2(bpy)2]2+/0 (c) [MCl2(bpy)]0; (d) [M(bpy)2]2+/0; (e) [Si(bpy)3]1+,0,1–,2–; and (f) [M(bpy)3]0 (M = C, Si, Ge, Sn, Pb) have been calculated using density functional theory (DFT). Where possible, geometry optimized structures are compared with their experimentally determined structures. In general, good to excellent agreement is observed. It is shown that the three successive one-electron reductions within the experimentally known series [Si(bpy)3]1+,0,1–,2– are ligand-based and the Si center has a +IV oxidation state throughout. Hence, these species have the electronic structures [SiIV(bpy•)3]+ (S = 1/2), [SiIV(bpy•)2(bpy2–)]0 (S = 0), [SiIV(bpy•)(bpy2–)2]− (S = 1/2), and [SiIV(bpy2–)3]2– (S = 0). Similarly, it is shown that the crystallographically characterized compound [Si(bpy)2]0 (S = 0) possesses the electronic structure [SiIV(bpy2–)2]0, which contains a tetravalent Si ion and two (bpy2–)2– dianions. It should not be described as [Si0(bpy0)2]0. For the heavier Ge, Sn, and Pb congeners the divalent state, characterized by a stereochemically active electron pair, becomes increasingly significant and dominates in 4-coordinate Sn and Pb species.
Keywords: | redox active ligands, redox non-innocence, main group complexes, Density functional theory calculations, Geometrical and electronic structures |
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Subjects: | F Physical Sciences > F170 Physical Chemistry F Physical Sciences > F120 Inorganic Chemistry |
Divisions: | College of Science > School of Chemistry |
ID Code: | 51914 |
Deposited On: | 11 Oct 2022 10:01 |
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