Synthesis, Structures, and Some Reactions of [(Thioacyl)thio]‐ and (Acylseleno)antimony and ‐bismuth Derivatives ((RCSS)xMR$\rm{_{{\bf 3 - }{\bf x}}^{\bf 1} }$ and (RCOSe)xMR$\rm{_{{\bf 3 - }{\bf x}}^{\bf 1} }$ with M = Sb, Bi and x = 1–3)

摘要: A series of [(thioacyl)thio]- and (acylseleno)antimony (acylseleno)bismuth, i.e., (RCSS)xMR (RCOSe)xMR (M = Sb, Bi, R1 = aryl, x = 1–3), were synthesized in moderate to good yields by treating piperidinium or sodium carbodithioates -selenoates with antimony bismuth halides. Crystal structures (4-MeC6H4CSS)2Sb(4-MeC6H4) (9b′), (4-MeOC6H4COSe)2Sb(4-MeC6H4) (12c′), (4-MeOC6H4COS)2Bi(4-MeC6H4) (15c′), (4-MeOC6H4CSS)2BiPh (18c) along (4-MeC6H4COS)2SbPh (6b) (4-MeC6H4COS)3Sb (7b) determined (Figs. 1 2). These compounds have a distorted square pyramidal structure, where the aryl carbothioato (= acylthio) ligand at central Sb- Bi-atom is perpendicular plane that includes two carbodithioato (= (thioacyl)thio), carboselenato (= acylseleno), exist as an enantiomorph pair. Despite large atomic radii, CS ⋅⋅⋅ Sb distances (RCSS)2MR1 (M = As, Sb, Bi; R1 = aryl) CO ⋅⋅⋅ Sb (RCOS)xMR x = 2, 3) are comparable shorter than those corresponding arsenic derivatives (Tables 2 3). molecular-orbital calculation performed on model (MeC(E)E1)3−xMMex E = O, S; E1 = S, Se; x = 1, 2) RHF/LANL2DZ level supported this shortening CE ⋅⋅⋅ Sb (Table 4). Natural-bond-orbital (NBO) analyses also revealed types orbital interactions nS  σ play role (thioacyl)thio (MeCSS)3−xMMex (x = 1, (Table 5). In acylthio-MeCOSMMe2 Bi), nO  σ contributes predominantly interactions, but MeCOSeSbMe2, none interactions. The greater acylthio acylseleno (MeCOE)3−xMMex (E = S, M = As, 2). ▪The reactions RCOSeSbPh2 (R = 4-MeC6H4) piperidine led formation diphenylselenoxoantimonate(1−) (= piperidinium diphenylstibinoselenoite) (H2NC5H10)+Ph2SbSe−, N-acylpiperidine (Table 6). Similar bis-derivatives (RCOSe)2SbR1 (R, R1 = 4-MeC6H4) gave novel di(piperidinium) phenyldiselenoxoantimonate(2−) (= di(piperidinium) phenylstibonodiselenoite), [(H2NC5H10)+]2(PhSbSe2)2−, which negative charges delocalized SbSe2 moiety Treatment RCOSeSbR N-halosuccinimides indicated Se-(halocyclohexyl) arenecarboselenoates (Table 8). Pyrolysis bis(acylseleno)arylbismuth 150° Se-aryl carboselenoates (Table 9).