title: Bismuth coordination chemistry with allyl, alkoxide, aryloxide, and tetraphenylborate ligands and the {[2,6-(Me2NCH2)2C6H3]2Bi}+ cation.
abstract: A series of bis(aryl) bismuth compounds containing (N,C,N)-pincer ligands, [2,6-(Me(2)NCH(2))(2)C(6)H(3)](-) (Ar'), have been synthesized and structurally characterized to compare the coordination chemistry of Bi(3+) with similarly sized lanthanide ions, Ln(3+). Treatment of Ar'(2)BiCl, 1, with ClMg(CH(2)CH═CH(2)) affords the allyl complex Ar'(2)Bi(η(1)-CH(2)CH═CH(2)), 2, in which only one allyl carbon atom coordinates to bismuth. Complex 1 reacts with KO(t)Bu and KOC(6)H(3)Me(2)-2,6 to yield the alkoxide Ar'(2)Bi(O(t)Bu), 3, and aryloxide Ar'(2)Bi(OC(6)H(3)Me(2)-2,6), 4, respectively, but the analogous reaction with the larger KOC(6)H(3)(t)Bu(2)-2,6 forms [Ar'(2)Bi][OC(6)H(3)(t)Bu(2)-2,6], 6, in which the aryloxide ligand acts as an outer sphere anion. Chloride is removed from 1 by NaBPh(4) to form [Ar'(2)Bi][BPh(4)], 5, which crystallizes from THF in an unsolvated form with tetraphenylborate as an outer sphere counteranion.
authors.affiliation: Department of Chemistry, University of California, Irvine, California 92697-2025, United States.
authors.forename: Ian J
authors.initials: IJ
authors.lastname: Casely
authors.forename: Joseph W
authors.initials: JW
authors.lastname: Ziller
authors.forename: Bruce J
authors.initials: BJ
authors.lastname: Mincher
authors.forename: William J
authors.initials: WJ
authors.lastname: Evans
mesh_terms: D000473:Alkanes / Q000737:chemistry*; D000498:Allyl Compounds / Q000737:chemistry*; D001729:Bismuth / Q000737:chemistry*; D002412:Cations; D018360:Crystallography, X-Ray; D006844:Hydrocarbons, Cyclic / Q000737:chemistry*; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010087:Oxides / Q000737:chemistry*; D013775:Tetraphenylborate / Q000737:chemistry*
chemical_list: D000473:Alkanes; D000498:Allyl Compounds; D002412:Cations; D006844:Hydrocarbons, Cyclic; D008024:Ligands; D009942:Organometallic Compounds; D010087:Oxides; D013775:Tetraphenylborate; D001729:Bismuth