The molecular and electronic structures of the 2,2'-bipyridine containing series of group 14 compounds (a) = 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 his a +IV oxidation state throughout., Hence; these species have the electronic structures [Si-IV(bpy)(3)](+) (S =1/2), [Si-IV.(bpy)(2)(bpy)(2))] (S = 0), " :[SP(bpr) (li:e7)2] (S. = 1/2), and [Sirv(bpy:27)3]2- (S Similarly,; it is shown that the crystallographically. characterized : compound [Si(bpy)(2)](0)(32(S.= 0) possesses the electronic structure [Si-IV(bpy(2-))(2)](0), which contains a tetravalent Si ion and two..,(bpy2-)2-' dianions: It should not be described as [Si (bpy)2]. 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.