Bismuth Coordination Chemistry with Allyl, Alkoxide, Aryloxide, and Tetraphenylborate Ligands and the {[2,6-(Me2NCH2)2C6H3]2Bi}+ Cation
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(CH2CHCH2) afford...
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Published in | Inorganic chemistry Vol. 50; no. 4; pp. 1513 - 1520 |
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Main Authors | , , , |
Format | Journal Article |
Language | English |
Published |
United States
American Chemical Society
21.02.2011
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Abstract | 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(CH2CHCH2) affords the allyl complex Ar′2Bi(η1-CH2CHCH2), 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. |
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AbstractList | 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. 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(CH2CHCH2) affords the allyl complex Ar′2Bi(η1-CH2CHCH2), 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. A series of bis(aryl) bismuth compounds containing (N,C,N)-pincer ligands, [2,6-(Me2NCH2)2C6H3]1- (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(?1-CH2CH=CH2), 2, in which only one carbon coordinates to bismuth. Complex 1 reacts with KOtBu and KOC6H3-2,6-Me2 to yield the alkoxide Ar'2Bi(OtBu), 3, and aryloxide Ar'2Bi(OC6H3-2,6-Me2), 4, respectively, but the analogous reaction with the sterically crowded KOC6H3-2,6-tBu2 forms [Ar'2Bi][OC6H3-2,6-tBu2], 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. |
Author | Casely, Ian J Ziller, Joseph W Mincher, Bruce J Evans, William J |
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Chem. doi: 10.1021/ic800667h contributor: fullname: Mincher B. J. |
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Snippet | 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... 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... A series of bis(aryl) bismuth compounds containing (N,C,N)-pincer ligands, [2,6-(Me2NCH2)2C6H3]1- (Ar'), have been synthesized and structurally characterized... |
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SubjectTerms | 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 |
Title | Bismuth Coordination Chemistry with Allyl, Alkoxide, Aryloxide, and Tetraphenylborate Ligands and the {[2,6-(Me2NCH2)2C6H3]2Bi}+ Cation |
URI | http://dx.doi.org/10.1021/ic102119y https://www.ncbi.nlm.nih.gov/pubmed/21192717 https://search.proquest.com/docview/851751711 https://www.osti.gov/biblio/1010692 |
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