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Шарутин, В. В.; Шарутина, О. К.; Егорова, И. В.; Ivanenko, T. K.; Bel’skii, V. K.

doi:10.1023/a:1015328925333

Cited by 8 publications

(13 citation statements)

References 2 publications

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“…The Bi‚‚‚F distance in 3 (2.971(2) Å) is ca. 20% shorter than the sum of van der Waals radii (3.75 Å) 25 and much longer than covalent Bi-F bond distances (2.190(4) Å in t BuN(CH 2 C 6 H 4 ) 2 Bi-F, 22 2.088-(8)-2.59(1) Å in the literature 18,21,[26][27][28][29][30][31][32] ). Weak interactions between the metals and fluorine atoms of fluorocarbons are well known.…”

Section: Resultsmentioning

confidence: 99%

Cationic Organobismuth Complex with 5,6,7,12-Tetrahydrodibenz[c,f][1,5]azabismocine Framework and Its Coordination Complexes with Neutral Molecules

2007

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A cationic eight-electron three-coordinate organobismuth complex with a weakly coordinating borate anion, [ t BuN(CH2C6H4)2Bi]+[B(C6F5)4]- (3), and its coordination complexes with neutral donor molecules were synthesized and structurally characterized. The reaction of t BuN(CH2C6H4)2Bi−X (1a: X = Br, 1b: X = Cl) with Li[B(C6F5)4] afforded the ionic complex 3. Complex 3 reacted with 1a or 1b to form halogen-bridged dinuclear complexes [{ t BuN(CH2C6H4)2Bi}2(μ-X)]+[B(C6F5)4]- (6: X = Br, 7: X = Cl). Various neutral donor molecules coordinated to the cationic bismuth atom of 3, and four coordination complexes [{ t BuN(CH2C6H4)2Bi}(Do)]+[B(C6F5)4]- (8: Do = MeCHO, 9: Do = MeOH, 10: Do = MeCN, 11: Do = CH2Cl2) were isolated. The structures of complexes 3 and 6−11 were determined by single-crystal X-ray analysis. In complex 3, one of the fluorine atoms of the [B(C6F5)4] anion weakly coordinates to the cationic bismuth center, making its coordination geometry equatorially vacant trigonal bipyramidal. The same coordination geometry was also found for the bismuth centers in 6−11. The cationic character of the bismuth center in 3 is reflected in the Bi−N coordination distance, which is ≥0.2 Å shorter than those in the neutral azabismocines such as 1a and 1b. The Bi−N coordination distances in 6−11 elongated depending on the coordination strength of the donor molecules.

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Section: Resultsmentioning

confidence: 99%

Cationic Organobismuth Complex with 5,6,7,12-Tetrahydrodibenz[c,f][1,5]azabismocine Framework and Its Coordination Complexes with Neutral Molecules

2007

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“…Ph 3 BiF 2 , is readily obtained by the treatment of Ph 3 Bi with XeF 2 . The condensation of 1 equiv.…”

Section: Resultsmentioning

confidence: 99%

“…A trigonal‐bipyramidal coordination geometry is observed around the cationic bismuth atom. Owing to the electron deficiency, the Bi–F bond lengths of the bismuthonium cation are shorter [ d (Bi–F1) = 224.7(3) and d (Bi–F1′) = 226.7(3) pm] than the Bi–F bond lengths of Ph 3 BiF 2 [average 259(1) pm] …”

Section: Resultsmentioning

confidence: 99%

Difluorotriorganylphosphoranes for the Synthesis of Fluorophosphonium and Bismuthonium Salts

et al. 2016

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Fluoride ion affinities (FIA), provided by DFT calculations, are exceedingly useful for the design of new Lewis acids with defined reactivities. Herein, we report the synthesis, characterization and reactivity of new difluoro(perfluoroorganyl)phosphoranes, which readily abstract fluoride ions from difluoro(triorganyl)phosphoranes. Highly reactive fluorobismuthonium cations and the [Ph3Bi(NCCH3)2]2+ cation are accessible through the treatment of difluoro(triorganyl)bismuth(V) compounds with the Lewis acidic phosphoranes discussed here.

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“…Surprisingly, 1 was found to be thermally stable in the solid state despite the presence of both the electrophilic phenyl group and the nucleophilic fluorine atom on the central bismuth. , Single-crystal X-ray diffraction analysis revealed that the bismuth center of 1 adopts a distorted trigonal bipyramidal geometry with three ipso carbons at the equatorial sites and one ipso carbon and fluorine atom at the apical sites (Figure ). − Indeed, the Bi−C ap bond length (2.260(6) Å) is longer than that of the Bi−C eq . The Bi−F bond length is 2.218(3) Å, which is shorter than the Bi−F bond of Ph 3 BiF 2 over 0.3 Å 1 ORTEP diagram of Ph 4 BiF ( 1 ).…”

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confidence: 86%

“…The Bi-F bond length is 2.218(3) Å, which is shorter than the Bi-F bond of Ph 3 BiF 2 over 0.3 Å. 10 Taking the unique amphiphilic property of 1 as well as the high affinity of fluorine toward silicon atom into consideration, 11 we examined the R-phenylation of ketones by the combination of 1 and enol silyl ethers (Scheme 1). Remarkably, mixing of 1 and 1-trimethylsiloxy-3,4-dihydronaphthalene in THF at -40 °C and stirring at room temperature for 10 min gave rise to 2-phenyl-1tetralone almost quantitatively without formation of the polyphenylated products (entry 1 in Table 1).…”

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confidence: 99%

Fluorotetraphenylbismuth: A New Reagent for Efficient Regioselective α-Phenylation of Carbonyl Compounds

2003

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Synthesis and X-ray crystallographic characterization of fluorotetraphenylbismuth (1) has been achieved for the first time, revealing that the bismuth center of 1 adopts a distorted trigonal bipyramidal geometry with three ipso carbons at the equatorial sites and one ipso carbon and fluorine atom at the apical sites. Contrary to the previous common understanding of this type of organobismuth(V) compound, 1 was found to be thermally stable, maintaining its amphiphilic property. Hence, 1 can be used as an off-the-shelf reagent in organic synthesis, and its utility has been clearly demonstrated in applications to the efficient alpha-phenylation of ketones and esters. For instance, simple mixing of 1 and 1-trimethylsiloxy-3,4-dihydronaphthalene in THF at -40 degrees C and stirring at room temperature for 10 min gave rise to 2-phenyl-1-tetralone almost quantitatively without formation of the polyphenylated products. In addition to the generality of this method, applicability of our approach to the selective alpha-alkenylation of carbonyl compounds was also demonstrated by the use of fluoro(2-phenylethenyl)tris(p-tolyl)bismuth (2) as a representative reagent. These results imply the vast potential of organobismuth(V) compounds of type 1 and 2 as useful precursors of a wide variety of pentavalent organobismuth compounds based on the utilization of the eminent fluorine-silicon interaction or the inherent basicity of the fluorine atom.

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Cited by 8 publications

References 2 publications

Cationic Organobismuth Complex with 5,6,7,12-Tetrahydrodibenz[c,f][1,5]azabismocine Framework and Its Coordination Complexes with Neutral Molecules

Cationic Organobismuth Complex with 5,6,7,12-Tetrahydrodibenz[c,f][1,5]azabismocine Framework and Its Coordination Complexes with Neutral Molecules

Difluorotriorganylphosphoranes for the Synthesis of Fluorophosphonium and Bismuthonium Salts

Fluorotetraphenylbismuth: A New Reagent for Efficient Regioselective α-Phenylation of Carbonyl Compounds

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