Organobismuth Research Articles

Electronic structure of organobismuth compounds: effective core potential and semiempirical calculations

Electronic structure of organobismuth compounds: effective core potential and semiempirical calculations

Synthesis and first X-ray structure analysis of a stabilized chiral chlorobismuthine: fixation of molecular geometry induced by the intramolecular coordination of a sulfonyl group

A sulfonyl-stabilized chiral chlorobismuthine 1a was synthesized by the selective fluorodearylation of compound 3a with boron trifluoride–diethyl ether, followed by halogen exchange of the resulting fluorobismuthine 4a with brine. The 1H NMR spectrum of compound 1a showed an unusually large downfield shift of a proton signal (δ 9.16), and X-ray structure analysis revealed that this unique shift was due to the anisotropic deshielding of the proton adjacent to the bismuth atom by the chlorine atom in close proximity. The bismuth centre of compound 1a was found to adopt a distorted pseudotrigonal bipyramidal geometry, probably through the formation of a hypervalent 3-centre 4-electron bond with the oxygen and chlorine atoms at apical positions. This is in marked contrast to the bismuthine 3a which has a pyramidal configuration characteristic of trivalent organobismuth compounds. A quite short Bi–O distance [2.592(5)A] of compound 1a, compared with that [2.914(6)A] of the bismuthine 3a, indicates that the introduction of an electronegative chlorine atom onto the bismuth atom enhances the Lewis acidity of the metal centre, leading to the pronounced intramolecular Bi-O interaction.

Synthesis and crystal structure of intramolecularly coordinated organobismuth compounds and edge inversion at trivalent bismuth

Synthesis and crystal structure of intramolecularly coordinated organobismuth compounds and edge inversion at trivalent bismuth

Secondary bonding in organobismuth compounds. Comparison of the structures of 2,2',5,5'-tetramethyl-1,1'-dibismaferrocene and 2,2',5,5'-tetramethylbibismole

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSecondary bonding in organobismuth compounds. Comparison of the structures of 2,2',5,5'-tetramethyl-1,1'-dibismaferrocene and 2,2',5,5'-tetramethylbibismoleArthur J. Ashe III, Jeff W. Kampf, Dhananjay B. Puranik, and Samir M. Al-TaweelCite this: Organometallics 1992, 11, 8, 2743–2745Publication Date (Print):August 1, 1992Publication History Published online1 May 2002Published inissue 1 August 1992https://doi.org/10.1021/om00044a003RIGHTS & PERMISSIONSArticle Views269Altmetric-Citations56LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (395 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Homogeneous radiopaque polymers with organobismuth compounds

AbstractThe effectiveness of triphenylbismuth and a few other bismuth compounds for use as a radiopacifying (X‐ray contrast) additive in polymeric materials was tested. Ph3Bi was found to be compatible (sometimes up to 70 wt %) with a wide range of monomers and polymers. It yields homogeneous mixtures with polystyrene, poly(vinyl chloride), polyacrylates, polyethylene, and other polymers. They can be formed by solvent casting, by melt processing, or by polymerizing a Ph3Bi/monomer mixture. Polymerization is not affected by the presence of Ph3Bi even when amine accelerators are used. Radiopacities of the polymer mixtures are proportional to the molar content of Ph3Bi, and can easily exceed that of aluminum. The bismuth compound lowers the Tg of PVC, PMMA, and polystyrene by 1.3°C/wt % Ph3Bi. The additive is moisture‐insensitive, water‐insoluble, and heat‐stable. It does not leach into water and has a low toxicity index. Leaching even in organic solvents can be prevented entirely by covalently binding bismuth to the polymer matrix through the use of monomers such as styryldiphenyl bismuth.

Simultaneous microdetermination of carbon, hydrogen, and bismuth in organobismuth compounds

A simple, rapid, and highly economical procedure is described for the simultaneous microdetermination of carbon, hydrogen, and bismuth in a large variety of 13 organobismuth compounds by applying the straight empty-tube method of Korshun-Klimova, which yielded results accurate to ±0.03%. The copresence of halogens, sulfur, and/or nitrogen proved to have no effect on the bismuth content as opposed to the case with antimony. The only interference on bismuth configuration is the co-occurrence of potassium on the same molecule.

ChemInform Abstract: Copper Salts Catalysis of N‐Phenylation of Amines by Trivalent Organobismuth Compounds.

Abstractp‐Anisidine (I) is phenylated with triphenyl bismuth (II) in the presence of Cu(II) acetate, forming the N‐monophenyl derivative (III).

Copper salts catalysis of N-phenylation of amines by trivalent organobismuth compounds

The N-arylation of aliphatic and aromatic amines by Ph 3Bi and Cu(OCOR) 2 gives high yield of the mono- or di-phenylated amines under mild conditions.

ChemInform Abstract: Copper Catalysed O‐Phenylation of Phenols and Enols by Pentavalent Organobismuth Compounds.

AbstractTriphenyl bismuth Compounds react with the phenol (IIa) in the presence of Cu‐derivatives yielding the O‐phenyl ether (IIb).

Copper catalysed [formula omitted]-phenylation of phenols and enols by pentavalent organobismuth compounds

The O -phenylation of phenols under neutral conditions by Bi V reagents is strongly catalysed by copper salts and by copper powder, even at room temperature. Enolic systems are also subject to copper powder catalysis and give exclusively O -phenylation.

Structural Studies of Crystalline Pentacalent Organobismuth Compounds

AbstractThe syntheses and X‐Ray analyses of three pentavalent organobismuth compounds are described; one of these compounds has a novel diphenylbis(trifluoroacetato)‐bismuthate anion with trigonal bipyramidal geometry and a stereochemically active lone pair. Analysis of these structures together with other data from the literature allows a mapping of the reaction coordinate for bismuth polyhedra.

Fungitoxicity of organoantimony and organobismuth compounds

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTFungitoxicity of organoantimony and organobismuth compoundsRobert E. Burrell, Charles T. Corke, and Ram G. GoelCite this: J. Agric. Food Chem. 1983, 31, 1, 85–88Publication Date (Print):January 1, 1983Publication History Published online1 May 2002Published inissue 1 January 1983https://doi.org/10.1021/jf00115a023RIGHTS & PERMISSIONSArticle Views127Altmetric-Citations13LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (457 KB) Get e-Alerts Get e-Alerts

Preparation, reactions, and physical properties of organobismuth compounds

Preparation, reactions, and physical properties of organobismuth compounds

Organobismuth compounds : X. Preparation and vibrational spectra of complexes of diphenylbismuth(III) derivatives

The cationic complex [Ph 2Bi(OAsPh 3) 2] + and the anionic complexes Ph 2BiX 2 −(X  Cl, Br, CN, SCN and N 3) have been prepared and their vibrational spectra have been investigated. The BiO stretching frequency for the cationic complex and the BiPh and BiX stretching frequencies for the anionic complexes have been assigned.

ChemInform Abstract: A (19)F NMR STUDY OF ELECTRONIC EFFECTS IN SOME ORGANOANTIMONY AND ORGANOBISMUTH COMPOUNDS CONTAINING METAL‐HETEROATOM BONDS

Chemischer InformationsdienstVolume 6, Issue 24 Physical Organic Chemistry ChemInform Abstract: A (19)F NMR STUDY OF ELECTRONIC EFFECTS IN SOME ORGANOANTIMONY AND ORGANOBISMUTH COMPOUNDS CONTAINING METAL-HETEROATOM BONDS D. N. KRAVTSOV, D. N. KRAVTSOVSearch for more papers by this authorB. A. KVASOV, B. A. KVASOVSearch for more papers by this authorS. I. POMBRIK, S. I. POMBRIKSearch for more papers by this authorE. I. FEDIN, E. I. FEDINSearch for more papers by this author D. N. KRAVTSOV, D. N. KRAVTSOVSearch for more papers by this authorB. A. KVASOV, B. A. KVASOVSearch for more papers by this authorS. I. POMBRIK, S. I. POMBRIKSearch for more papers by this authorE. I. FEDIN, E. I. FEDINSearch for more papers by this author First published: June 17, 1975 https://doi.org/10.1002/chin.197524074AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume6, Issue24June 17, 1975 RelatedInformation

A 19F NMR study of electronic effects in some organo-antimony and organobismuth compounds containing metal—heteroatom bonds

The 19F NMR technique has been used to study the ground-state electronic effects of univalent organo-antimony and -bismuth substituents in compounds of the type (C 6H 5) n MSC 6H 4F-3, (C 6H 5) n MSC 6H 4F-4, (C 6H 5) 4SbOC 6H 4F-3, (C 6H 5) 4SbOC 6H 4F-4 and (4-FC 6H 4) 2SbX, where (C 6H 5) n M = (C 6H 5) 2Sb, (C 6H 5) 2Bi and (C 6H 5) 4Sb, X = C 6H 5S, CH 3COO, Cl, Br. It has been found that the electron-donating effect of the sulphur-containing groups increases in the order: (C 6H 5) 2SbS < (C 6H 5) 2BiS < (C 6H 5) 4SbS, the substituents (C 6H 5) 4SbS and (C 6H 5) 4SbO being the most electron-releasing among the (C 6H 5) n MS and (C 6H 5) n MO groups containing heavy non-transition metals. From the viewpoint of solvent susceptibility of their electronic effects the (C 6H 5) 2SbS, (C 6H 5) 2BiS and (C 6H 5) 4SbS groups resemble the (C 6H 5) 3SnS and (C 6H 5) 3PbS substituents, and differ from the C 6H 5HgS group, whereas the (C 6H 5) 4SbO substituent differs in this respect from all other (C 6H 5) n MO groups. The low conjugating ability of the (C 6H 5) 2SbS substituent and slight influence of steric hindrance upon its electronic effect have been explained by the operation of conformational factors. It has been established that the electronic interactions across the antimony—heteroatom bonds are mainly of inductive character and that the order of electron withdrawal for the ArSbX substituents can be reversed on transfer from an inert to coordinating solvent.

Organobismuth compounds. VI. Preparation and characterization of cationic complexes of triphenylbismuth(V) derivatives

Organobismuth compounds. VI. Preparation and characterization of cationic complexes of triphenylbismuth(V) derivatives

Organobismuth(V) compounds. Part VII. Preparation, characterization, and vibrational spectra of four- and five-co-ordinate tetraphenylbismuth(V) derivatives

New tetraphenylbismuth(V) compounds Ph4BiX (X = BF4, PF6, NCO, NCS, and CCl3CO2) have been prepared. These compounds, together with the previously known Ph4BiClO4 and Ph4BiN03, have been studied Oby i.r. and laser Raman spectroscopy and by molecular-weight and conductance measurements. The vibrational spectra and conductance data for the derivatives, where X = ClO4, BF4, or PF6, are consistent with an ionic constitution. The nitrate, trichloroacetate, thiocyanate, and cyanate compounds are indicated to be non-ionic, containing five-co-ordinate bismuth. Molecular-weight data for the nitrate and trichloroacetate compounds, in benzene, are also in accord with a five-co-ordinate structure; the thiocyanate and the cyanate compounds decompose in benzene. Assignments for vibrational frequencies associated with the Bi–Ph bonds for the ionic and five-co-ordinate derivatives are discussed.

The 1H nuclear magnetic resonance spectra of some organobismuth compounds

The 1H nuclear magnetic resonance spectra of some organobismuth compounds

Organobismuth Compounds. III. Preparation and Infrared Spectra of Triphenylbismuth(V) Derivatives of Dibasic Acids

Triphenylbismuth carbonate, oxalate, sulfate, selenate, and chromate have been prepared and their solid state infrared (i.r.) spectra have been studied in the frequency region 4000 to 200 cm−1. The i.r. spectroscopic results indicate that, like the corresponding trimethyl- and triphenylantimony(V) derivatives, these compounds also have non-ionic polymeric structures containing bridging anion groups and five co-ordinate bismuth. The i.r. frequencies associated with the bismuth–anion stretching vibrations appear to occur at 300 cm−1 for the carbonate and below 300 cm−1 for the other compounds.