Thioacylsulfanylarsines (RCS2)(x)AsPh3-x, x = 1-3: synthesis, structures, natural bond order analyses and reactions with piperidine

Citation
K. Tani et al., Thioacylsulfanylarsines (RCS2)(x)AsPh3-x, x = 1-3: synthesis, structures, natural bond order analyses and reactions with piperidine, J CHEM S DA, (5), 2001, pp. 518-527
Citations number
67
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Inorganic & Nuclear Chemistry
Journal title
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
ISSN journal
1472-7773 → ACNP
Issue
5
Year of publication
2001
Pages
518 - 527
Database
ISI
SICI code
1472-7773(2001):5<518:T(X=1S>2.0.ZU;2-2
Abstract
A series of thioacylsulfanylarsines ((RCS2)AsPh2, (RCS2)(2)AsPh, (RCS2)(3)A s) were synthesized by treating piperidinium dithiocarboxylates with Ph2AsC l, PhAsCl2 or AsCl3, respectively and characterized. Their molecular struct ures were determined by X-ray crystallography and compared with those of th e corresponding acylsulfanyl derivatives ((RCOS)AsPh2, (RCOS)(2)AsPh, (RCOS )(3)As). They exist as monomers, and the environment around the arsenic ato ms is distorted tetrahedral with one lone pair at the apex. The structure o f the mono(dithiocarboxylate) is different from that of the corresponding t hiocarboxylic acid derivative, while the bis and tris derivatives showed si milar structure to the corresponding thiocarboxylic acid derivatives ((RCOS )(2)AsPh, (RCOS)(3)As), respectively. The new compounds showed intramolecul ar interactions between the thiocarbonyl sulfur and the central arsenic ato m. NBO (Natural Bond Orbital) analyses performed on the model compounds (CH 3CS2)As(CH3)(2) and (CH3CS21)(CH3CS22)AsCH3 at the RHF/LANL2DZ level of the ory showed the presence of interactions between the non-bonding orbitals on the thiocarbonyl sulfur (n(S)) and the sigma*(MS) orbitals together with t hat between the n(S) and the sigma*(MC) orbitals for the former compound; f or the latter the presence of both orbital interactions between n(S) and si gma*(MS1) and between n(s) and sigma*(MS2) are present. The reaction of the mono(dithiocarboxylate) derivative (R epsilon=epsilon4-CH3C6H4) with piper idine in ethanol gave piperidinium diphenyldithioarsinate along with the co rresponding N-thioacyl- or N-acyl-piperidine. A similar reaction of the bis (dithiocarboxylate) derivative (R epsilon=epsilon4-CH3C6H4) gave the novel di(piperidinium) phenyltrithioarsonate in which two anion charges are deloc alized on the AsS3 moiety and a cyclic phenylarsine sulfide tetramer (PhAsS )(4). The diphenyldithioarsinate and phenyltrithioarsonate salts exist as a dimer and a polymer, respectively, in which 12-membered rings are formed b y intermolecular N-H . . .S hydrogen bonds.