Reactivity of molecules containing element-element bonds. 1. Nontransition elements

Calderazzo, Fausto; Morvillo, Antonino; Pelizzi, Giancarlo; Poli, Rinaldo; Ungari, Fausto

doi:10.1021/ic00294a012

Cited by 48 publications

(39 citation statements)

References 2 publications

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“…[61] Concerning the conformation of the molecules the most noticeable difference is the torsion angles about the E-Te bond. The orientation of the ethyl groups in Et 2 SbTeEt is T-shaped as was previously observed for Ph 2 BiSePh, [22] whereas it is Y-shaped in Et 2 BiTeEt (figure 2, cisoid conformation (C-Bi-C-C 165.5(7)°, 45.0(9)°).…”

Section: R 2 Mer' (M = Sb Bi; E = Se Te)supporting

confidence: 65%

“…[81,46] M a n u s c r i p t Unfortunately, the crystal quality of Bi(SeTrip) 3 was too low to allow a detailed structure discussion. Bi(SePh) 3 crystallizes with two independent molecules in the asymmetric unit and forms a trigonal-pyramidal structure as was observed for Sb(SeMe) 3 [57] Ph 2 BiSePh (2.704(3) Å), [22] and Bi(SeR) 3 (R = 2-(4,4-dimethyloxazolino)phenyl, 2.6910(8), 2.7049(9), 2.7454(9) Å). [58] Moreover, the terminal Bi-Se bond lengths as-observed in the polynuclear bismuthselenolates, [Bi 4 (μ-SePh) 5 (SePh) 8 ] − (2.646(4)-2.737(4) Å) and [Bi 6 (μ-SePh) 6 (SePh) 10 Br 2 ]…”

Section: Rm(er') 2 (M = Sb Bi; E = Se Te)mentioning

confidence: 59%

“…[56] However, the most convenient route for such compounds including those containing sterically less demanding organic substituents, for which intermolecular interactions between adjacent molecules in the solid state are most likely, are reactions of low-valent dipentelanes R 4 M 2 (M = Sb, Bi) containing weak M-M bonds with dichalcogenanes E' 2 R 2 (E' = S, Se, Te). [8,10,18,19,20,21,22] For instance, R 2 SbER' (E = S, Se, Te; R = Me, Et, R' = Me, Ph) were obtained from reactions of Sb 2 R 4 and E 2 R' 2 at ambient temperature (Sb 2 Me 4 ) and -40 °C (Sb 2 Et 4 ), respectively. [15,16,17] R 2 SbTeMe (R = Me, Et), which decompose upon heating with formation of the corresponding trialkylstibine SbR 3 and RSb(ER') 2 , were reported to be thermochromic, indicating the presence of intermolecular contacts between the metal centers in the solid state.…”

Section: R 2 Mer' (M = Sb Bi; E = Se Te)mentioning

confidence: 99%

“…[57] These compounds were found to decompose in solution with elimination of Bi(EPh) 3 [22] and Bi(SeR) 3 (R = 2-(4,4-dimethyloxazolino)phenyl, 2.6910(8), 2.7049(9), 2.7454(9) Å ), [58] the only structurally characterized compounds containing a Bi-Se single bond, as well as with the sum of the covalent radii ∑ cov (Bi,E) = 2.67 (E = Se), and 2.87 Å (E = Te) as reported by…”

Section: R 2 Mer' (M = Sb Bi; E = Se Te)mentioning

confidence: 99%

“…Surprisingly, Ph 2 BiSePh showed an even smaller bond angular sum at the Bi center (275.6°). [22] A c c e p t e d M a n u s c r i p t 9 Figure 2. Solid state structure of Et 2 SbTeEt; thermal ellipsoids are shown at 50% probability levels.…”

Section: R 2 Mer' (M = Sb Bi; E = Se Te)mentioning

confidence: 99%

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Covalently bonded compounds of heavy group 15/16 elements – Synthesis, structure and potential application in material sciences

Schulz

2015

Coordination Chemistry Reviews

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Section: R 2 Mer' (M = Sb Bi; E = Se Te)supporting

confidence: 65%

Section: Rm(er') 2 (M = Sb Bi; E = Se Te)mentioning

confidence: 59%

Section: R 2 Mer' (M = Sb Bi; E = Se Te)mentioning

confidence: 99%

Section: R 2 Mer' (M = Sb Bi; E = Se Te)mentioning

confidence: 99%

Section: R 2 Mer' (M = Sb Bi; E = Se Te)mentioning

confidence: 99%

See 3 more Smart Citations

Covalently bonded compounds of heavy group 15/16 elements – Synthesis, structure and potential application in material sciences

Schulz

2015

Coordination Chemistry Reviews

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Bismuth: Organometallic Chemistry

Whitmire

2005

Encyclopedia of Inorganic Chemistry

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Bismuth readily forms a variety of tri‐ and pentavalent organic derivatives by the reactions of bismuth halides with Grignard, organolithium, organozinc, or organoaluminum reagents. Bismuth(III) triaryl compounds are readily oxidized by chlorine and bromine to triaryl dihalides, while iodine reacts to produce aryl bismuth iodides. Some organobismuth compounds are Lewis acidic, showing the ready formation of higher coordination number adducts with traditional ligands. A variety of organobismuth compounds with bismuth–bismuth and bismuth–transition metal bonds are described. Organobismuth(V) have found uses as selective oxidants and aryl transfer reagents.

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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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Reactivity of molecules containing element-element bonds. 1. Nontransition elements

Cited by 48 publications

References 2 publications

Covalently bonded compounds of heavy group 15/16 elements – Synthesis, structure and potential application in material sciences

Covalently bonded compounds of heavy group 15/16 elements – Synthesis, structure and potential application in material sciences

Bismuth: Organometallic Chemistry

Bismuth Compounds

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