7065-21-6Relevant articles and documents
Synthesis and Crystal and Molecular Structure of Tetraphenyldibismuthine, Bi2Ph4, the First Crystallographically Characterized Tetraorganyl Derivative of Bismuth(II)
Calderazzo, Fausto,Morvillo, Antonio,Pelizzi, Giancarlo,Poli, Rinaldo
, p. 507 - 508 (1983)
Tetraphenyldibismuthine, Bi2Ph4, was prepared by reducing BiPh2Cl with sodium in liquid ammonia and characterized by conventional methods, including X-ray diffractometry.
Comprehensive Study on Reactions of Group 13 Diyls with Tetraorganodipentelanes
Ganesamoorthy, Chelladurai,Krüger, Julia,Gl?ckler, Eduard,Helling, Christoph,John, Lukas,Frank, Walter,W?lper, Christoph,Schulz, Stephan
, p. 9495 - 9503 (2018/08/17)
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.
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
Cassidy, Juanita M.,Whitmire, Kenton H.
, p. 2788 - 2795 (2008/10/08)
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?.
