2,2'-bipyridine compounds of group 14 elements: A density functional theory study

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

Full text not available from this repository.

Item Type:Article
Item Status:Live Archive


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
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

Repository Staff Only: item control page