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

作者：Casely Ian J; Ziller Joseph W; Mincher Bruce J; Evans William J^*

来源：Inorganic Chemistry, 2011, 50(4): 1513-1520.

DOI：10.1021/ic102119y

A series of bis(aryl) bismuth compounds containing (N,C,N)-pincer ligands, [2,6-(Me2NCH2)(2)C6H3](-) (Ar'), have been synthesized and structurally characterized to compare the coordination chemistry of Bi3+ with similarly sized lanthanide ions, Ln(3+). Treatment of Ar-2'BiCl, 1, with ClMg(CH2CH=CH2) affords the allyl complex Ar-2'Bi(eta(1)-CH2CH=CH2), 2, in which only one allyl carbon atom coordinates to bismuth. Complex 1 reacts with (KOBu)-Bu-t and KOC6H3Me2-2,6 to yield the alkoxide Ar-2'Bi((OBu)-Bu-t), 3, and aryloxide Ar-2'Bi(OC6H3Me2-2,6), 4, respectively, but the analogous reaction with the larger (KOC6H3Bu2)-Bu-t-2,6 forms [Ar-2'Bi][(OC6H3Bu2)-Bu-t-2,6], 6, in which the aryloxide ligand acts as an outer sphere anion. Chloride is removed from 1 by NaBPh4 to form [Ar-2'Bi][BPh4], 5, which crystallizes from THF in an unsolvated form with tetraphenylborate as an outer sphere counteranion.

• 出版日期2011-2-21