- Synthesis and Crystal and Molecular Structure of Tetraphenyldibismuthine, Bi2Ph4, the First Crystallographically Characterized Tetraorganyl Derivative of Bismuth(II)
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Tetraphenyldibismuthine, Bi2Ph4, was prepared by reducing BiPh2Cl with sodium in liquid ammonia and characterized by conventional methods, including X-ray diffractometry.
- Calderazzo, Fausto,Morvillo, Antonio,Pelizzi, Giancarlo,Poli, Rinaldo
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- Indirect Access to Carbene Adducts of Bismuth- And Antimony-Substituted Phosphaketene and Their Unusual Thermal Transformation to Dipnictines and [(NHC)2OCP][OCP]
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The synthesis and thermal redox chemistry of the first antimony (Sb)- and bismuth (Bi)-phosphaketene adducts are described. When diphenylpnictogen chloride [Ph2PnCl (Pn = Sb or Bi)] is reacted with sodium 2-phosphaethynolate [Na[OCP]·(dioxane)x], tetraphe
- Walley, Jacob E.,Warring, Levi S.,Kertész, Erik,Wang, Guocang,Dickie, Diane A.,Benk?, Zoltán,Gilliard, Robert J.
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p. 4733 - 4743
(2021/04/06)
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- Comprehensive Study on Reactions of Group 13 Diyls with Tetraorganodipentelanes
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L1Ga {L1 = HC[C(Me)N(2,6-iPr2C6H3)]2} reversibly reacts with E2Ph4 (E = Sb, Bi) in a temperature-dependent equilibrium reaction with insertion into the E-E bond and formation of L1Ga(EPh2)2 (E = Sb 1, Bi 2). Analogous findings were observed in the reactions of L2Ga {L2 = (C6H11)2NC[N(2,6-iPr2C6H3)]2} with E2R4 (R = Ph, Et), yielding L2Ga(EPh2)2 (E = Sb 3, Bi 4) and L2Ga(EEt2)2 (E = Sb 5, Bi 6). 1-3 and 5 were isolated by fractional crystallization at low temperature, whereas 4 and 6 could not be isolated in their pure form even at low temperature. In contrast, reactions of [Cp?Al]4 (Cp? = C5Me5) with Sb2R4 (R = Ph, Et) and Bi2Et4 did not proceed with insertion into the E-E bonds but with formation of (Cp?Al)3E2 (E = Sb, 7; Bi, 8), whereas the reaction with Bi2Ph4 yielded metallic bismuth. 8 was also formed in the reaction of [Cp?Al]4 and BiEt3 at ambient temperature, whereas the analogous reaction of [Cp?Al]4 with SbEt3 did not yield 7 even under drastic reaction conditions (120 °C, 3 days). In contrast, Cp?Ga and Sb2R4 (R = Ph, Et) were found to react only at elevated temperature (120 °C) with formation of antimony metal.
- Ganesamoorthy, Chelladurai,Krüger, Julia,Gl?ckler, Eduard,Helling, Christoph,John, Lukas,Frank, Walter,W?lper, Christoph,Schulz, Stephan
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p. 9495 - 9503
(2018/08/17)
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- REACTIVITY OF MOLECULES CONTAINING ELEMENT-ELEMENT BONDS. PART III. REDUCTION OF HALO-ORGANOMETALLICS OF ANTIMONY(III) AND BISMUTH(III); CRYSTAL AND MOLECULAR STRUCTURE OF CoCp2
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Tetraphenyldibismuthine has been prepared by reducing BiPh2I with bis (cyclopentadienyl)-cobalt(II).CoCp2, the former being produced in situ in THF solution from BiPh3 and BiI3 (2:1 molar ratio) or from BiPh3 and I2; also, bis(pentamethylcyclopentadienyl)cobalt(II), CoCp2, reduces BiPh2Cl to Bi2Ph4 in THF solution.The bismuth(III) bromides Bi(p-tolyl)2Br or BiMe2Br have been reduced by CoCp2 to the corresponding dibismuthines, Bi2(p-tolyl)4 or Bi2Me4.Reduction by CoCp2 of the chloro derivatives of bismuth(III) and antimony(III), EPh2Cl produces E2Ph4 and the ionic CoCp2 complexes as by-products.The crystal and molecular structure of the antimony derivative CoCp2 was solved by X-ray diffraction methods.Crystal data: monoclinic, space group P21, a = 8.856(3), b = 16.245(5), c = 7.770(3) Angstroem, β = 109.67(5) deg, Z = 2, R = 0.0396.Similar to Bi2Ph4, Sb2Ph4 undergoes reactions across the element-element bond with p-benzoquinone and diazomethane to the corresponding insertion products (Ph2Sb)2O2C6H4 and (Ph2Sb)2CH2, respectively.
- Calderazzo, Fausto,Marchetti, Fabio,Ungari, Fausto,Wieber, Markus
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- Syntheses and structures of the phenylbismuth/transition-metal carbonyl compounds [PPN][Ph2BiFe(CO)4], (Ph2Bi)2Fe(CO)4, [PhBiFe(CO)4]2, and Ph2BiMn(CO)5
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Treatment of Na2Fe(CO)4 with 1 equiv of Ph2BiCl in tetrahydrofuran (THF) affords Na[Ph2BiFe(CO)4], characterized as the [PPN]+ (PPN = bis(triphenylphosphine)nitrogen(1+)) salt ([PPN][I]); adding a second 1 equiv of Ph2BiCl produces (Ph2Bi)2Fe(CO)4 (II), which decomposes to [PhBiFe(CO)4]2 (III) in solution. III is also obtained in poor yield from the reaction of PhBiBr2 and Na2Fe(CO)4·3/2diox (diox = dioxane) in THF. The reduction of Ph2BiCl with 2 equiv of sodium in liquid NH3 followed by addition of Fe(CO)5 yields II and III along with traces of Ph4Bi2. I, II, and III·CH2Cl2 have been characterized by single-crystal X-ray diffraction. Crystals of [PPN][I] are monoclinic, Cc (No. 9), with a = 13.08 (1) A?, b = 15.832 (9) A?, c = 23.18 (1) A?, β = 99.53 (6)°, V = 4733 (6) A?3, and Z = 4. Convergence was achieved with R = 5.8% and Rw = 6.0% for 2584 observed reflections. The iron atom has a trigonal-bipyramidal coordination geometry with the pyramidal Ph2Bi group occupying an axial position. The Bi-Fe distance is 2.676 (4) A?. II crystallizes in the monoclinic space group P21/n (No. 14) with a = 12.009 (3) A?, b = 13.074 (2) A?, c = 17.264 (2) A?, β = 96.78 (1)°, V = 2691.5 (8) A?3, and Z = 4. The structure was refined to R = 5.0% and Rw = 5.8% for 3698 observed reflections. The octahedral Fe(CO)4 group in II is bonded to two Ph2Bi groups in cis positions. The average Bi-Fe distance in this compound is 2.828 (6) A?. III·CH2Cl2 crystallizes in the monoclinic crystal system, space group C2/c (No. 15) with a = 17.681 (6) A?, b = 7.069 (2) A?, c = 21.573 (10) A?, β = 101.19(3)°, V = 2645 (2) A?3, and Z = 4. The structure was refined to R = 4.2% and Rw = 4.9% for 1821 reflections with I > 3σ(I). The structure consists of a Bi2Fe2 planar parallelogram situated about an inversion center with an average Bi-Fe distance of 2.786 (3) A?. Each bismuth atom is bonded to one phenyl group. The iron carbonyl groups exhibit cis-pseudooctahedral coordination environments. The reaction of Ph2BiX (X = Cl, I) with Na[Mn(CO)5] produces octahedral Ph2BiMn(CO)5 (IV), which crystallizes in the triclinic space group P1 (No. 2) with a = 10.135 (4) A?, b = 13.484 (4) A?, c = 6.567 (4) A?, α = 99.11 (3)°, β = 92.53 (4)°, γ = 86.46 (2)°, V = 883.9 (6) A?3, Z = 2, R = 4.4%, and Rw = 5.6% for 2036 observed reflections. The Bi-Mn distance is 2.842 (2) A?.
- Cassidy, Juanita M.,Whitmire, Kenton H.
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p. 2788 - 2795
(2008/10/08)
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- Reactivity of molecules containing element-element bonds. 1. Nontransition elements
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A new method for preparing Bi2Ph4 consists of reducing BiPh2I with bis(cyclopentadienyl)cobalt(II) in tetrahydrofuran as solvent, with yields as high as 80%. The mixed products Ph2BiEPh (E = S, Se, Te) were obtained by reacting Bi2Ph4 with E2Ph2 in toluene as solvent at room temperature. The crystal and molecular structure of BiSePh3 has been solved. Crystal data: C18H15BiSe, Mr = 519.3, orthorhombic, space group P212121, a = 15.936 (3) ?, b = 11.550 (3) ?, c = 8.855 (2) ?, Z = 4, d(calcd) = 2.116 g cm-3. The structure consists of tricoordinated and bicoordinated bismuth and selenium, respectively, paired by a Bi-Se bond 2.704 (3) ? long. The tellurium and selenium mixed species undergo diazomethane insertion with formation of the Ph2Bi-CH2-EPh species. Tetraphenyldibismuthine is oxidized by elemental selenium, giving (BiPh2)2Se.
- Calderazzo, Fausto,Morvillo, Antonino,Pelizzi, Giancarlo,Poli, Rinaldo,Ungari, Fausto
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p. 3730 - 3733
(2008/10/08)
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- Synthesis, Reactivity, and Crystal and Molecular Structure of Tetraphenyldibismuth, Bi2Ph4
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Tetraphenyldibismuth, Bi2Ph4, is best prepared by the reaction of BiPh2I with 1 equivalent of sodium in liquid ammonia, followed by extraction with toluene and recrystallization from anhydrous ethanol.It is sensitive to air and slightly thermocromic.The crystal and molecular structure was solved by X-ray diffraction methods: triclinic, space group , with a=7.865(4), b=11.444(5) c=6.257(3) Angstroem, α=105.24(4), β=94.20(7), γ=96.52(6) deg, and Z=1; R=0.0560 for 1 097 absorption-corrected reflections having I>=3?(I).The molecule has a staggered trans conformation, with bismuth-bismuth distance of 2.990(2) Angstroem.Tetraphenyldibismuth reacts promptly with di-iodine to give BiPh2I, and with p-benzoquinne, elemental sulphur, and diazomethane to give the corresponding products of bismuth(III) resulting from oxidative insertion into the bismuth-bismuth bond.
- Calderazzo, Fausto,Poli, Rinaldo,Pelizzi, Giancarlo
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p. 2365 - 2370
(2007/10/02)
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- Transition Metal Carbene Complexes, CXXXI. Reaction of BF4 with Anionic Organyl Compounds of Group V Elements
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The cationic carbyne complex BF4 (1) reacts with potassiumdiphenylamide, KNPh2, with nucleophilic addition of the amide anion to give (CO)5W (2).The corresponding reactions with KPPh2, KPEt2, KPMePh, NaSbPh2 and NaBiPh2 yield the complex 2 (3), which is formed by reductive dimerization of two carbyne fragments.In case of KPMePh the carbene complexes (CO)5W (5) are also obtained.On warming in solution 5 spontaneously rearranges to the novel cyclic carbene complex (CO)4WPMePh (6).Reaction conditions, properties and spectroscopic data of the new compounds are reported. - Keywords: Transition Metal Carbene Complexes
- Fischer, Ernst Otto,Reitmeier, Rudolf
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p. 582 - 586
(2007/10/02)
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- Preparation and properties of dibismuthines
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Tetramethyldibismuthine, 1, tetraisopropenyldibismuthine, 15, 1,1′-bibismolane, 16, and tetrakis(2-methyl-1-propenyl)dibismuthine, 17, have been prepared from the reaction of the corresponding tertiary bismuthines with sodium in liquid ammonia followed by treatment with 1,2-dichloroethane. Tetraphenyldibismuthine, 4, was prepared by an analogous route from diphenylbismuth chloride. While all the dibismuthines are red in solution, 1, 15, and 16 freeze to blue solids. Compounds 4 and 17 form red solids. The Raman, UV, and mass spectra of the dibismuthines are discussed. The dibismuthines thermally decompose to form bismuth metal and corresponding tertiary bismuthine. The reactions of tetramethyldibismuthine with iodine, bromotrichloromethane, benzyl bromide, hydrochloric acid, and butyllithium have been explored. The reactions afford products in which the Bi-Bi bond has been cleaved.
- Ashe III, Arthur J.,Ludwig Jr., Edward G.,Oleksyszyn, Josef
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p. 1859 - 1866
(2008/10/08)
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- SPALTUNG VON TRIPHENYLBISMUTAN MIT KALIUM. BILDUNG VON TETRAPHENYLDIBISMUTAN UND DIPHENYL(ETHYL)BISMUTAN
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Cleavage of Ph3Bi with K in tetrahydrofuran gives Ph2BiK and PhK.Ph2BiK reacts with ClCH2CH2Cl to form Ph2BiBiPh2.Ph2BiEt is obtained from Ph2BiK and EtBr.
- Breunig, Hans Joachim,Mueller, Ditmar
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p. C21 - C22
(2007/10/02)
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