Synthesis and Molecular Structure of Decamethyl-1,4- dibismutha-2,3,5,6,7-pentasilabicyclo[2.2.1]heptane

Kollegger, Gerlinde M.; Siegl, Harald; Haßler, Karl; Gruber, Karl

doi:10.1021/om960308s

Cited by 10 publications

(35 citation statements)

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“…Only seventeen examples of such species, whose structures have been determined by X-ray diffraction, are well-known up to now. Primarily, these are homonuclear [1][2][3] (four examples) and heteronuclear [1,3,[5][6][7][8][9][10][11] complexes (thirteen examples) containing silyl groups of various steric requirements [SiMe 3 , SitBu 3 , Si(SiMe 3 ) 3 ], which play a stabilizing role here. In these compounds, bismuth displays the oxidation states +1, +2 and +3.…”

Section: Introductionmentioning

confidence: 99%

“…In these compounds, bismuth displays the oxidation states +1, +2 and +3. Homo-and heteronuclear silyl-substituted bismuth complexes could be obtained by different synthetic strategies: (a) metalation of trisilylbismuthane with alkyllithium, [1] (b) conversion of lithium bis(trisilylbismuthane) with 1,2-dibromoethane, [1] (c) conversion of sodium potassium bismuthide with 1,2-dichlorotetramethyldisilane, [2] (d) reduction of bismuth halides with alkali metal silanides [3] and with silyl-substituted lithium phos-322 bond in the dibismuthane unit and a shortening of the intermolecular Bi···Bi contacts. According to MP4(SDQ) computations, such oligomerization is carried out by intermolecular interaction of s lone pairs that are bound together and p-type orbitals of the Bi-Bi bonds in the bismuth chain.…”

Section: Introductionmentioning

confidence: 99%

“…According to MP4(SDQ) computations, such oligomerization is carried out by intermolecular interaction of s lone pairs that are bound together and p-type orbitals of the Bi-Bi bonds in the bismuth chain. An increase in the number of [(H 3 Si) 2 Bi] 2 molecules per chain results in a decrease in the HOMO-LUMO gap and leads to a bathochromic shift. TD-PBE0 computations suggest that the lowest energy electron transition in 2 is metal-metal charge transfer.…”

Section: Introductionmentioning

confidence: 99%

“…TD-PBE0 computations suggest that the lowest energy electron transition in 2 is metal-metal charge transfer. In addition, the attractive contributions in the chain [(H 3 A) 2 -Bi] 2 ···[Bi(AH 3 ) 2 ] 2 with silyl groups (A = Si) outweigh the repulsion of the Bi···Bi centers, whereas for the alkyl-substituted bismuth chain (A = C) the repulsive van der Waals force dominates. This fact makes the rectangle oligomerization model more preferred for n[(H 3 A) 2 Bi] 2 (A = C; n = 2), while for A = Si chain formation is favored in the gas phase.…”

Section: Introductionmentioning

confidence: 99%

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Reduction vs. Metathesis in the Reactions of Bismuth Tribromide with a Bulky Lithium Silanide – An Experimental and Theoretical Study

2010

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Keywords: Bismuth / Silicon / Lithium / Crystal structure analysis / Density functional calculations On reaction of BiBr 3 with Li(thf) 3 SiPh 2 tBu (1) in the corresponding ratios redox/metathesis reactions were observed, yielding dibismuthane (tBuPh 2 Si) 4 Bi 2 (2) and disilylbismuth halide (tBuPh 2 Si) 2 BiBr (3). The latter is a reaction intermediate in the formation of the dark-red 2. The X-ray crystal structures of 1-3 were determined by low-temperature X-ray diffraction. The Si 2 Bi-BiSi 2 core of 2 is in the semi-eclipsed conformation. No oligomerization of "nonthermochromic" 2 was observed. Compound 3 is a mixed substituted monomer with a pyramidal environment around the bismuth center. On the basis of quantum chemical calculations, the formation of tertiary bismuthane (tBuPh 2 Si) 3 Bi is not expected for steric reasons. According to DFT-optimized geometries of the simplified model systems n[(H 3 Si) 2 Bi] 2 (n = 1-3), the closed-shell attraction between intermolecular Bi centers in the chain provides a moderate elongation of the intramolecular Bi-Bi

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Reduction vs. Metathesis in the Reactions of Bismuth Tribromide with a Bulky Lithium Silanide – An Experimental and Theoretical Study

2010

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“…Si 91.56 265.22 [15] Bi(CH 2 SiMe 3 ) 3 94.03 (C-Bi-C) - [16] [a] Average values. All cage structures possess two three-coordinate pnicogen atoms with pyramidal geometry of the ESi 3 core.…”

Section: Compoundmentioning

confidence: 99%

Synthesis and Coordination of the Cagelike Siloxane Compounds E₂{(SiMe₂)₂O}₃ (E = As, Sb, Bi)

et al. 2013

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Keywords: Silicon / Siloxanes / Cage compounds / PnicogensThe cage compounds [E 2 {(SiMe 2 ) 2 O} 3 ] for E = P, As, Sb, and Bi (1, 4, 5, and 6, respectively) are readily accessible in moderate yields by the reaction of Na 3 E (for E = P, As, Sb, Bi) or [Li(dme)EH 2 ] (for E = P, As; dme = dimethoxyethane) with 1,3-dichloro-1,1,3,3-tetramethyldisiloxane.These compounds were isolated and characterized by X-ray crystallographic analysis. The major structural parameters such as the E-Si bond length and the Si-E-Si angles are discussed and compared with those of similar compounds. The small Si-ESi angles in these compounds are attributable to steric and electronic reasons. Further, the R 3 M-E[(SiMe 2 ) 2 O] 3 E-MR 3

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Bismuth Compounds

Breunig

2002

Kirk-Othmer Encyclopedia of Chemical Technology

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Bismuth is the fifth member of the nitrogen family of elements and like its congeners possesses five electrons in its outermost shell, (6 s 2 )(6 p 3 ). In many compounds, the bismuth atom utilizes only the three 6 p electrons in bond formation and retains the two 6 s electrons as an inert pair. Compounds are also known where bismuth is bonded to four, five, or six other atoms. Many bismuth compounds do not have simple molecular structures and exist in the solid state as polymeric chains or sheets. Inorganic compounds of bismuth include bismuthine, bismuthides, bismuth halides, bismuth oxide halides, bismuth oxides and bismuthates, higher oxides of bismuth and related compounds, sulfides and related compounds, and bismuth salts. In a manner similar to phosphorus, arsenic, and antimony, the bismuth atom can be either tri‐ or pentacovalent. Methylbismuthine, CH 3 BiH 2 , and dimethylbismuthine, (CH 3 ) 2 BiH, are prepared by the lithium aluminum hydride reduction of methyldichlorobismuthine, CH 3 BiCl 2 , and dimethylchlorobismuthine, respectively. Tertiary bismuthines appear to have a number of uses in synthetic organic chemistry and for a number of other industrial purposes. Chloro‐, dichloro‐, bromo‐, and dibromobismuthines are best prepared by the reaction of a tertiary bismuthine and bismuth trichloride or tribromide. Tetraalkyl‐ and tetraaryldibismuthines can be obtained by the reaction of a sodium dialkyl‐ or diarylbismuthide and a 1,2‐dihaloethane. Dibismuthines tend to be thermally unstable. They also are very sensitive to oxidation. Organobismuth(V) compounds have found considerable use as oxidizing agents. After the tertiary bismuthines, the triarylbismuth dihalides constitute the most important class of organobismuth compounds and are by far the largest class of compounds containing pentacovalent bismuth. Very few trialkylbismuth dihalides have been prepared. In addition to use in organic synthesis and limited industrial use, triarylbismuth dihalides have been used as catalysts for the carbonation of epoxides to form cyclic carbonates. A number of bismuthonium ylides, have been prepared and their reactions studied. A number of pentaarylbismuth compounds are known. Pentaphenylbismuth, C 30 H 25 Bi, is a violet‐colored, crystalline compound that decomposes spontaneously after standing for several days in a dry nitrogen atmosphere. It has been studied as a reagent in organic synthesis where it can act either as an oxidizing or an arylating agent. Commercially available preparations of Bismuth subsalicylate (Pepto‐Bismol), a basic salt of varying composition, corresponding approximately to o ‐HOC 6 H 4 CO 2 (BiO), and De‐Nol, tripotassium dicitratobismuthate (bismuth subcitrate) are applied in the treatment of duodenal ulcers, gastritis and diarrhea.

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Synthesis and Molecular Structure of Decamethyl-1,4- dibismutha-2,3,5,6,7-pentasilabicyclo[2.2.1]heptane

Cited by 10 publications

References 5 publications

Reduction vs. Metathesis in the Reactions of Bismuth Tribromide with a Bulky Lithium Silanide – An Experimental and Theoretical Study

Reduction vs. Metathesis in the Reactions of Bismuth Tribromide with a Bulky Lithium Silanide – An Experimental and Theoretical Study

Synthesis and Coordination of the Cagelike Siloxane Compounds E₂{(SiMe₂)₂O}₃ (E = As, Sb, Bi)

Bismuth Compounds

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Synthesis and Molecular Structure of Decamethyl-1,4- dibismutha-2,3,5,6,7-pentasilabicyclo[2.2.1]heptane

Cited by 10 publications

References 5 publications

Reduction vs. Metathesis in the Reactions of Bismuth Tribromide with a Bulky Lithium Silanide – An Experimental and Theoretical Study

Reduction vs. Metathesis in the Reactions of Bismuth Tribromide with a Bulky Lithium Silanide – An Experimental and Theoretical Study

Synthesis and Coordination of the Cagelike Siloxane Compounds E2{(SiMe2)2O}3 (E = As, Sb, Bi)

Bismuth Compounds

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Synthesis and Coordination of the Cagelike Siloxane Compounds E₂{(SiMe₂)₂O}₃ (E = As, Sb, Bi)