Bismuth(III) coordination compounds.: Synthesis, characterization, and X-ray structures of [Bi(Cl)(μ-Cl)2(THF)2]∞, Bi(O2CMe)3(Solv)x (Solv = py, x = 2 or MeIm, x = 4) [1], and [Bi(μ-O CH2CMe3)(OCH2CMe3)2(Solv)]2 (Solv = HOCH2CMe3 or py)

We have isolated and structurally characterized several novel bismuth coordination compounds. Dissolution of Bi(NO3)(3) . 5H(2)O in concentrated HCl, followed by crystallization from THF lead to the isolation of [Bi(Cl)(mu-Cl)(2)(THF)(2)](infinity), 1. Each bismuth metal center of 1 adopts a 7-coordinated pentagonal bipyramidal geometry. One THF solvent molecule and one terminal chloride ligand are located in each of the axial positions. A terminal THF solvent molecule and four bridging chlorides reside in the equatorial positions. Dissolution of Bi(O2CMe)(3) in pyridine (py) or N-methylimidazole (MeIm) results in the isolation of the appropriate amine adduct, either Bi(O2CMe)(3)(py)(2), 2 or Bi(O2CMe)(3)(MeIm)(3) .(MeIm), 3. Compound 2 uses two py molecules to adopt an unusual (for bismuth acetate species) 8-coordinated triangular dodecahedral geometry. In contrast, 3 incorporates three MeIm molecules to adopt the 9-coordinated tricapped trigonal prismatic geometry typically observed for bismuth acetate compounds (a "free" MeIm molecule is located in the lattice). The reaction of Bi[N(SiMe3)(2)](3) with HOCH2CMe3 (HONp) yields [Bi(mu-ONp)(ONp)(2)(HONp)](2), 4. An alternative synthetic route to 4 is the metathical exchange between BiCl3 and 3 equivalents of NaONp in the presence of HONp. The bismuth atoms of 4 are 5-coordinated and adopt an apical-shared, square base pyramidal (SP) arrangement. Recrystallization of 4 from py yields the dinuclear complex [Bi(mu-ONp)(ONp)(2)(py)](2), 5. The Bi atoms of 5 also adopt a 5-coordinated SP geometry; however, the two metal centers are linked through a basal-shared arrangement. The apical ONp ligands are in an up-down relationship to each other. (C) 1998 Elsevier Science Ltd. All rights reserved.