Mixed triorganobismuthines RAr₂Bi [Ar = C₆F₅, 2,4,6-(C₆F₅)₃C₆H₂] and hypervalent racemic Bi-chiral diorganobismuth(iii) bromides RArBiBr (Ar = C₆F₅, Mes, Ph) with the ligand R = 2-(Me₂NCH₂)C₆H₄. Influences of the organic substituent

Abstract

Triorganobismuthines R(C6F5)2Bi (1) and R[2,4,6-(C6F5)3C6H2]2Bi (2) [R = 2-(Me2NCH2)C6H4] were synthesized by reaction of RBiBr2 with C6F5MgBr and 2,4,6-(C6F5)3C6H2Li, respectively, in a 1 : 2 molar ratio. The Bi-chiral bromides R(C6F5)BiBr (3), R(Mes)BiBr (4), and R(Ph)BiBr (5) were obtained from RBiBr2 and C6F5MgBr, MesMgBr or PhMgBr, or from PhBiBr2 and RLi, in a 1 : 1 molar ratio. The molecular structures of 1-5 were determined by single-crystal X-ray diffraction and are discussed taking into account the chirality of the species. Supramolecular aspects in the solid state are presented. The solution behaviour of the title compounds, including dynamic aspects, are discussed on the basis of multinuclear ((1)H, (13)C, (19)F) NMR spectroscopy.

Organic Compounds of Bismuth: Synthesis, Structure, and Applications

“…The organobismuth compounds with the N,C-aryl ligand LBi(Ph)Cl and LMPh 2 were synthesized in high yields from aryllithium dichloride LBiCl 2 (L = o-(СH=N-Dipp)C 6 H 4 ) and phenyllithium in a ratio of 1 : 1 or 1 : 2 (Scheme 10) [11]. Li, respectively, at the 1 : 2 molar ratio [12]. Bromides R(C 6 F 5 )BiBr, R(Mes)BiBr, and R(Ph)BiBr were synthesized from the equimolar amounts of RBiBr 2 and C 6 F 5 MgBr, MesMgBr, or PhMgBr or from PhBiBr 2 and RLi in the 1 : 1 molar ratio.…”

“…Other triorganylbismuth compounds (Scheme (12) Å at the sum of the van der Waals radii of bismuth and sulfur equal to 3.8 Å) [20].…”

“…Bromides R(C 6 F 5 )BiBr, R(Mes)BiBr, and R(Ph)-BiBr (R = 2-(Me 2 NCH 2 )C 6 H 4 ) were synthesized similarly from equimolar amounts of RBi-Br 2 and C 6 F 5 MgBr, MesMgBr, or PhMgBr or from PhBiBr 2 and RLi in a molar ratio of 1 : 1 (Scheme 89) [12]. In the monochlorides, one nitrogen atom is strongly coordinated to the bismuth atom (2.660 (11) The reactions of organobismuth(III) chlorides R 2 BiCl and RBiCl 2 , where R = 2-(Me 2 NCH 2 )C 6 H 4 , with alkaline metal pseudohalides in a molar ratio of 1 : 1 and 1 : 2, respectively, afforded hypervalent bismuth compounds R 2 BiX (X = NCO, SeCN) and RBiX 2 (X = NCO, NCS, and SeCN) (Scheme 95) [98].…”

Synthesis and structure of 6-diphenylphosphinoacenaphth-5-yl bismuth compounds

“…1 Alternatively, the donor ligands may also bind to transition metal ions giving rise to interesting complexes that involve metal bismuth interactions. The vast majority of these ligands possess Ndonors, [2][3][4][5][6][7][8] whereas as P-donors are only occasionally encountered. [9][10][11][12][13][14][15] As part of our research programme on peri-substituted scaffolds, we recently prepared the monoarylbismuth dichloride RBiCl 2 (1a, R = 6-diphenylphosphinoacenaphth-5-yl), the analogous arylantimony dichloride RSbCl 2 (1b) 16 as well as the diarylantimony chloride R 2 SbCl (2b) and the triarylantimony R 3 Sb (3b).…”

One-Pot Synthesis of Hypervalent Diaryl(iodo)bismuthanes from o-Carbonyl Iodoarenes by Zincation

“…Much effort has been devoted to the study of hypervalent bismuth(III) compounds [1][2][3][4][5]. Hypervalent bonds are formed efficiently via intramolecular coordination of a neutral donor to a bismuth(III) center [6][7][8][9][10][11][12]. We have used this method to synthesize various hypervalent organobismuth(III) compounds stabilized by intramolecular coordination and have characterized their molecular structures [13].…”