On the reactivity of less common halopseudohalogens towards metalcarbon- and metalmetal-bonded compounds

Raj, Prem; Kiran, Shumaila; Rastogi, R. P.

doi:10.1016/s0277-5387(00)84419-8

Cited by 23 publications

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“…As expected for a highly endothermic, binary covalent polyazide, Te(N 3 ) 4 is very sensitive and can explode violently. Its identity was established by the observed material balance, and through vibrational and NMR spectroscopy.…”

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confidence: 79%

“…It is, therefore, not surprising that polyazides are highly endothermic compounds, and that their energy content increases with an increasing number of azido ligands. Compared to the relatively stable azide anion, which possesses two double bonds, the bonds in covalent azides are polarized towards a single and a triple bond, which greatly facilitates N 2 elimination and enhances their shock sensitivity.Consequently, the synthesis and characterization of covalent binary azides containing multiple azido ligands can present great experimental challenges, and binary tellurium azides are no exception to this general rule.Whereas numerous, partially azide-substituted tellurium compounds have been reported, [1][2][3][4][5][6][7][8][9][10][11][12][13][14] only one binary tellurium azide, the [Te(N 3 ) 3 ] + ion, has previously been reported. [5] In this paper, we wish to communicate the synthesis and characterization of three novel binary tellurium azides, In the presence of catalytic amounts of CsF, the reaction of TeF 6 with excess (CH 3 ) 3 SiN 3 in acetonitrile solution at room temperature results in the reduction of Te VI to Te IV , while the azide ion is oxidized to dinitrogen.…”

mentioning

confidence: 99%

“…Whereas numerous, partially azide-substituted tellurium compounds have been reported, [1][2][3][4][5][6][7][8][9][10][11][12][13][14] only one binary tellurium azide, the [Te(N 3 ) 3 ] + ion, has previously been reported. [5] In this paper, we wish to communicate the synthesis and characterization of three novel binary tellurium azides, In the presence of catalytic amounts of CsF, the reaction of TeF 6 with excess (CH 3 ) 3 SiN 3 in acetonitrile solution at room temperature results in the reduction of Te VI to Te IV , while the azide ion is oxidized to dinitrogen.…”

mentioning

confidence: 99%

“…[5] In this paper, we wish to communicate the synthesis and characterization of three novel binary tellurium azides, Te(N 3 ) 4 , [Te(N 3 ) 5 ] À , and [Te(N 3 ) 6 ] 2À .…”

mentioning

confidence: 99%

“…Furthermore, complete fluoride-azide exchange takes place, to yield a clear yellow solution of Te(N 3 ) 4 according to Equation (1).…”

mentioning

confidence: 99%

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Polyazide Chemistry: Preparation and Characterization of Te(N₃)₄ and [P(C₆H₅)₄]₂[Te(N₃)₆] and Evidence for [N(CH₃)₄][Te(N₃)₅]

et al. 2003

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The azido group is highly energetic and adds about 70 kcalmol À1 to the energy content of a molecule. It is, therefore, not surprising that polyazides are highly endothermic compounds, and that their energy content increases with an increasing number of azido ligands. Compared to the relatively stable azide anion, which possesses two double bonds, the bonds in covalent azides are polarized towards a single and a triple bond, which greatly facilitates N 2 elimination and enhances their shock sensitivity.Consequently, the synthesis and characterization of covalent binary azides containing multiple azido ligands can present great experimental challenges, and binary tellurium azides are no exception to this general rule.Whereas numerous, partially azide-substituted tellurium compounds have been reported, [1][2][3][4][5][6][7][8][9][10][11][12][13][14] only one binary tellurium azide, the [Te(N 3 ) 3 ] + ion, has previously been reported. [5] In this paper, we wish to communicate the synthesis and characterization of three novel binary tellurium azides, In the presence of catalytic amounts of CsF, the reaction of TeF 6 with excess (CH 3 ) 3 SiN 3 in acetonitrile solution at room temperature results in the reduction of Te VI to Te IV , while the azide ion is oxidized to dinitrogen. Furthermore, complete fluoride-azide exchange takes place, to yield a clear yellow solution of Te(N 3 ) 4 according to Equation (1).Removal of the volatile products (CH 3 CN, (CH 3 ) 3 SiF, and excess (CH 3 ) 3 SiN 3 ) in vacuo results in the isolation of Te(N 3 ) 4 as a bright-yellow solid. In the absence of CsF, no fluorideazide exchange reaction was observed even after several days at room temperature. The catalytic function of the fluoride ion in these reactions probably involves the generation of intermediate free azide ions from the reaction of (CH 3 ) 3 SiN 3 and F À ions, and these free azide ions might be the actual reagent. The need for fluoride-ion catalysis, found in our study, is in contrast to the results from a previous 19 F NMR study [9] in which TeF 6 was reported to undergo facile fluorideazide exchange with (CH 3 ) 3 SiN 3 in CD 3 CN solution to produce all the members of the TeF n (N 3 ) 6Àn (n = 1-5) series. In their study, these authors also observed the azide-ionmediated reduction of Te VI to Te IV as a side reaction.As expected for a highly endothermic, binary covalent polyazide, Te(N 3 ) 4 is very sensitive and can explode violently. 125 Te shifts are in accord with our expectations for a multi-azido-substituted Te IV compound; the shift reported for the closest known analogue, CH 3 Te(N 3 ) 3 , is d = 1405 ppm. [12] Furthermore, the presence of covalent azido ligands [11][12][13][14][15][16] is confirmed by the observed 14 N NMR shifts of d = À139.8 ppm (N b , Dn 1/2 = 63 Hz) and À238 ppm (N g , Dn 1/2 = 680 Hz) in DMSO solution at 25 8C. In addition to quadrupolar broadening, rapid ligand exchange on the NMR timescale by the Berry pseudorotation mechanism [17] might contribute to the observation of only one set ...

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mentioning

confidence: 79%

mentioning

confidence: 99%

mentioning

confidence: 99%

“…[5] In this paper, we wish to communicate the synthesis and characterization of three novel binary tellurium azides, Te(N 3 ) 4 , [Te(N 3 ) 5 ] À , and [Te(N 3 ) 6 ] 2À .…”

mentioning

confidence: 99%

“…Furthermore, complete fluoride-azide exchange takes place, to yield a clear yellow solution of Te(N 3 ) 4 according to Equation (1).…”

mentioning

confidence: 99%

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Polyazide Chemistry: Preparation and Characterization of Te(N₃)₄ and [P(C₆H₅)₄]₂[Te(N₃)₆] and Evidence for [N(CH₃)₄][Te(N₃)₅]

et al. 2003

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Bismuth Compounds

Long¹,

Freedman²,

Doak³

2000

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. One primary and one secondary bismuthine, methylbismuthine, CH 3 BiH 2 , and dimethylbismuthine, (CH 3 ) 2 BiH, respectively, 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. Two trialkylbismuth dihalides have been prepared, cis ‐tripropenylbismuth dibromide, C 9 H 15 BiBr 2 , and trans ‐tripropenylbismuth dibromide, C 9 H 15 BiBr 2 . 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. Antibiotics have made bismuth compounds completely obsolete for the treatment of syphilis. Bismuth subsalicylate, Pepto‐Bismol, is a basic salt of varying composition, corresponding approximately to o ‐HOC 6 H 4 CO 2 (BiO). Like a number of other insoluble bismuth preparations, it is not currently approved in the United States for the treatment of peptic ulcer disease but is under active investigation for this purpose. It does appear to be effective for the relief of mild diarrhea and for the prevention of travelers' diarrhea. Bismuth subcarbonate (basic bismuth carbonate) is a white or pale yellow powder that has been widely used as an antacid. De‐Nol, tripotassium dicitratobismuthate (bismuth subcitrate), is said to be very effective for the treatment of gastric and duodenal ulcers. Bismuth subnitrate (basic bismuth nitrate) has been used as an antacid and in combination with iodoform as a wound dressing. Bismuth subgallate (basic bismuth gallate), Dermatol, a bright yellow powder has been employed as a dusting powder in some skin disorders and for the treatment of hemorrhoids.

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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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On the reactivity of less common halopseudohalogens towards metalcarbon- and metalmetal-bonded compounds

Cited by 23 publications

References 26 publications

Polyazide Chemistry: Preparation and Characterization of Te(N₃)₄ and [P(C₆H₅)₄]₂[Te(N₃)₆] and Evidence for [N(CH₃)₄][Te(N₃)₅]

Polyazide Chemistry: Preparation and Characterization of Te(N₃)₄ and [P(C₆H₅)₄]₂[Te(N₃)₆] and Evidence for [N(CH₃)₄][Te(N₃)₅]

Bismuth Compounds

Bismuth Compounds

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On the reactivity of less common halopseudohalogens towards metalcarbon- and metalmetal-bonded compounds

Cited by 23 publications

References 26 publications

Polyazide Chemistry: Preparation and Characterization of Te(N3)4 and [P(C6H5)4]2[Te(N3)6] and Evidence for [N(CH3)4][Te(N3)5]

Polyazide Chemistry: Preparation and Characterization of Te(N3)4 and [P(C6H5)4]2[Te(N3)6] and Evidence for [N(CH3)4][Te(N3)5]

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Polyazide Chemistry: Preparation and Characterization of Te(N₃)₄ and [P(C₆H₅)₄]₂[Te(N₃)₆] and Evidence for [N(CH₃)₄][Te(N₃)₅]

Polyazide Chemistry: Preparation and Characterization of Te(N₃)₄ and [P(C₆H₅)₄]₂[Te(N₃)₆] and Evidence for [N(CH₃)₄][Te(N₃)₅]