Bismuth Coordination Chemistry with Allyl, Alkoxide, Aryloxide, and Tetraphenylborate Ligands and the {[2,6-(Me2NCH2)2C6H3]2Bi}+ Cation

• Published in: Inorganic chemistry Vol. 50; no. 4; pp. 1513 - 1520
• Main Authors: Casely, Ian J, Ziller, Joseph W, Mincher, Bruce J, Evans, William J
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 21.02.2011
• Subjects: Alkanes - chemistry; ALKOXIDES; Allyl Compounds - chemistry; BISMUTH; Bismuth - chemistry; BISMUTH COMPOUNDS; CARBON; CATIONS; CHEMISTRY; CHLORIDES; coordination chemistry; Crystallography, X-Ray; Hydrocarbons, Cyclic - chemistry; lanthanides; Ligands; Magnetic Resonance Spectroscopy; NUCLEAR FUEL CYCLE AND FUEL MATERIALS; Organometallic Compounds - chemical synthesis; Organometallic Compounds - chemistry; Oxides - chemistry; RARE EARTHS; Tetraphenylborate - chemistry
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic102119y

A series of bis(aryl) bismuth compounds containing (N,C,N)-pincer ligands, [2,6-(Me2NCH2)2C6H3]− (Ar′), have been synthesized and structurally characterized to compare the coordination chemistry of Bi3+ with similarly sized lanthanide ions, Ln3+. Treatment of Ar′2BiCl, 1, with ClMg(CH2CHCH2) affords the allyl complex Ar′2Bi(η1-CH2CHCH2), 2, in which only one allyl carbon atom coordinates to bismuth. Complex 1 reacts with KOtBu and KOC6H3Me2-2,6 to yield the alkoxide Ar′2Bi(OtBu), 3, and aryloxide Ar′2Bi(OC6H3Me2-2,6), 4, respectively, but the analogous reaction with the larger KOC6H3 tBu2-2,6 forms [Ar′2Bi][OC6H3 tBu2-2,6], 6, in which the aryloxide ligand acts as an outer sphere anion. Chloride is removed from 1 by NaBPh4 to form [Ar′2Bi][BPh4], 5, which crystallizes from THF in an unsolvated form with tetraphenylborate as an outer sphere counteranion.