Lucia Balázs

Syntheses and crystal structures of a covalent trialkylantimony hydroxo bromide and related trialkylantimony(V) halides

R 3 SbBr 2 ( 1 ), RMe 2 SbBr 2 ( 2 ), or RMe 2 SbI 2 ( 3 ) [R=(Me 3 Si) 2 CH] are formed by addition of Br 2 or I 2 to R 3 Sb or RMe 2 Sb. (Me 3 SiCH 2 ) 3 Sb(Br)OH ( 4 ) is obtained by hydrolyzing 1 or (Me 3 SiCH 2 ) 3 SbBr 2 . The crystal structures of 1 , 3 , 4 and [(Me 3 SbBr) 2 ]O ( 5 ) [Me=CH 3 ] have been determined.

Hypervalent 5–Bi–12 derivatives containing dichalcogenoimidodiphosphinato ligands. Crystal structure and solution behaviour of [2-(Me2NCH2)C6H4]BiCl[(XPR2)(YPR′2)N](X, Y = O, S, Se; R, R′= Me, Ph)

The reaction between [2-(Me2NCH2)C6H4]BiCl2 and M[(XPR2)(YPR′2)N] in 1 ∶ 1 molar ratio affords the new functionalised [2-(Me2NCH2)C6H4]BiCl[(XPR2)(YPR′2)N] derivatives [R = Me, R′ = Ph, X = O, Y = S (1); R = R′ = Ph, X = Y = S (2), Se (3)]. Variable-temperature NMR studies suggest a fluxional behaviour in solution. The investigation of the molecular structures of 1–3 by single-crystal X-ray diffraction revealed that the N atoms of the pendant CH2NMe2 arm are strongly coordinated to the Bi atom and the organophosphorus ligands act as a bidentate moiety through both chalcogens, thus resulting in a square pyramidal coordination geometry around the metal atoms. The analysis of the crystal packing of 2 and 3 reveals the presence of pairs of enantiomers (the metal center is chiral) associated through weak intermolecular Bi⋯Cl interactions. The crystal of 1 contains only the trans-O–Bi–Cl isomer as a 1 ∶ 1 mixture of the two enantiomers, in a unique square pyramidal (C,N)BiCl(O,S) coordination geometry with five different atoms attached to the metal atom.

ORGANOBISMUTH HOMOCYCLES (RBi)n AND HETEROCYCLES (RBiS)2

The homocycles (RBi)n (n = 3–5) react with MeC5 H4Mn(CO)2(thf) (thf = tetrahydrofuran) or Fe2(CO)9 to give Bi2[Mn(CO)2MeC5 H4]3 (1) or Bi2Fe3(CO)9 (3). Reaction of R4Bi2 (R = Me3SiCH2) with Fe2(CO)9 in toluene gives R2Bi2Fe2(CO)8 (4) and R4Bi2Fe(CO)4 (5). The heterocycles (RBiS)2(R = 2-(Me2NCH2)C6 H4 (6), 2, 6-(Me2NCH2)2 C6 H4 (7) are formed by reaction of the corresponding dihalides RBiCl2 with Na2S. The reaction of (RBiS)2(R = 2-(Me2NCH2)C6 H4) with W(CO)5(thf) leads to (RBiS)2[W(CO)5]2 (8).

Syntheses of isobutylantimony compounds, cyclo-RnSbn (n = 4, 5), R4Sb2, and crystal structure of R3SbBr2; R = Me2CHCH2

Abstract Dehalogenation reactions of RSbBr2 or R2SbBr (R=Me2CHCH2) with Mg in tetrahydrofuran give cyclo-RnSbn (1, n=4, 5) or R4Sb2 (2). R3SbBr2 (3) is formed by addition of Br2 to R3Sb. The crystals of 3 consist of trigonal bipyramidal molecules with apical bromine atoms.

Synthese und Kristallstruktur von Tetramesityldibismutan / Synthesis and Crystal Structure of Tetramesityldibismuthane

Tetramesityldibismuthane is obtained by the reaction of Mes2BiCl (Mes = 2,4,6-(CH3)3C6H2) and LiEH4 (E = B, Al) with intermediate formation of Mes2BiH. Crystals of Mes4Bi2 consist of centrosymmetric tetramesityldibismuthane molecules in the trans conformation. The value of the Bi-Bi bond length is 3.087(3) Å .