The Lewis acidity of organylbismuth(III) compounds. New organylbismuth(III) dithiocarbamate chemistry. The crystal and molecular structure of bis(diethyidithiocarbamato)phenylbismuth(III) and bis(diethyldithiocarbamato)-[2-(2′-pyridyl)phenyl]bismuth(III)

Abstract

The Lewis Acidity of Organylbismuth(iii) Compounds. New Organylbismuth(iii) Dithiocarbamate Chemistry. The Crystal and Molecular Structure of Bis-(diethyldithiocarbamato)phenylbismuth(iii) and Bis(diethy1dithiocarbamato)-[2-(2'-pyridyl)phenyl] bismuth( 1 1 1 ) *

The First Example of a Structurally Characterized Monomeric Bismuth Selenolate

“…11 This contrasts with the bismuth^sulfur distances reported for bis(diethyldithiocarbomato)[2-(2 H -pyridyl)phenyl]bismuth(iii) in which the Bi^S distances are longer than the expected values. 12 As expected, the NÁ Á ÁBi distances, N(1)Á Á ÁBi 2.952(6), N(2)Á Á ÁBi 2.827(7), N(3)Á Á ÁBi 2.884(6) Ð, are much longer than the sum of the single bond covalent radii of nitrogen and bismuth (2.22 Ð) but are well within the van der Waals distance. 11 These distances are also signi¢cantly longer than the NÁ Á ÁBi distance reported for bis(diethyldithiocarbomato)[2-(2 H -pyridyl)phenyl]bismuth(iii) 12 and lie at the upper end of the range reported for the same interactions in other bismuth compounds 13 which lie in the range 2.56^2.86 Ð.…”

“…12 As expected, the NÁ Á ÁBi distances, N(1)Á Á ÁBi 2.952(6), N(2)Á Á ÁBi 2.827(7), N(3)Á Á ÁBi 2.884(6) Ð, are much longer than the sum of the single bond covalent radii of nitrogen and bismuth (2.22 Ð) but are well within the van der Waals distance. 11 These distances are also signi¢cantly longer than the NÁ Á ÁBi distance reported for bis(diethyldithiocarbomato)[2-(2 H -pyridyl)phenyl]bismuth(iii) 12 and lie at the upper end of the range reported for the same interactions in other bismuth compounds 13 which lie in the range 2.56^2.86 Ð. The NÁ Á ÁBi interactions are, therefore, considered as secondary in nature.…”

Main Group Dithiocarbamate Complexes

“…Bis(dithiocarbamate) complexes of the type [MR(S 2 CNR 2 ) 2 ] and [MX(S 2 CNR 2 ) 2 ] (M ¼ As, Sb, or Bi; R ¼ alkyl, aryl, or organometallic group; X ¼ halide) have also been studied extensively (212,213,219,224,241,248,(253)(254)(255)(256)(257)(258)(259)(260)(261)(262)(263)(264)(265)(266)(267)(268)(269)(270). The organyl complexes are prepared by reaction of the metal dihalides, RMX 2 , with the appropriate dithiocarbamate salt (253, 254, 260-263, 266, 268).…”

“…The dimers are formed by the side-on docking of the [MR(S 2 CNR 2 ) 2 ] units (Fig. 19), such that the two metal and eight S atoms are essentially coplanar (255,260,261). The dithiocarbamate ligands are best considered as anisobidentate: The asymmetry in the MÀ ÀS bonding decreases as the size of the metal increases.…”

“…The equatorial plane contains the four S atoms plus the nitrogen atom, with the C(phenyl) atom and stereochemically active lone pair in the axial positions (Fig. 20) (261).…”