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(CH2CHCH2) afford...

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Published inInorganic 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
LanguageEnglish
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
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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(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.
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(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.
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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https://www.osti.gov/biblio/1010692$$D View this record in Osti.gov
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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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acs
SourceType Open Access Repository
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StartPage 1513
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
Volume 50
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