Synthesis, Structures, and Some Reactions of [(Thioacyl)thio]- and (Acylseleno)antimony and -bismuth Derivatives ((RCSS)xMR and (RCOSe)xMR with M = Sb, Bi and x = 1–3)
✍ Scribed by Mitsutoshi Kimura; Akiyuki Iwata; Masahiro Itoh; Kazuki Yamada; Tsutomu Kimura; Noriyuki Sugiura; Masaru Ishida; Shinzi Kato
- Publisher
- John Wiley and Sons
- Year
- 2006
- Tongue
- German
- Weight
- 674 KB
- Volume
- 89
- Category
- Article
- ISSN
- 0018-019X
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✦ Synopsis
Abstract
A series of [(thioacyl)thio]‐ and (acylseleno)antimony and [(thioacyl)thio]‐ and (acylseleno)bismuth, i.e., (RCSS)~x~MR$\rm{_{3 - x}^1 }$ and (RCOSe)~x~MR$\rm{_{3 - x}^1 }$ (M = Sb, Bi, R^1^ = aryl, x = 1–3), were synthesized in moderate to good yields by treating piperidinium or sodium carbodithioates and ‐selenoates with antimony and bismuth halides. Crystal structures of (4‐MeC~6~H~4~CSS)~2~Sb(4‐MeC~6~H~4~) (9b′), (4‐MeOC~6~H~4~COSe)~2~Sb(4‐MeC~6~H~4~) (12c′), (4‐MeOC~6~H~4~COS)~2~Bi(4‐MeC~6~H~4~) (15c′), and (4‐MeOC~6~H~4~CSS)~2~BiPh (18c) along with (4‐MeC~6~H~4~COS)~2~SbPh (6b) and (4‐MeC~6~H~4~COS)~3~Sb (7b) were determined (Figs. 1 and 2). These compounds have a distorted square pyramidal structure, where the aryl or carbothioato (= acylthio) ligand at the central Sb‐ or Bi‐atom is perpendicular to the plane that includes the two carbodithioato (= (thioacyl)thio), carboselenato (= acylseleno), or carbothioato ligand and exist as an enantiomorph pair. Despite the large atomic radii, the CS ⋅⋅⋅ Sb distances in (RCSS)~2~MR^1^ (M = As, Sb, Bi; R^1^ = aryl) and the CO ⋅⋅⋅ Sb distances in (RCOS)~x~MR$\rm{_{3 - x}^1 }$ (M = As, Sb, Bi; x = 2, 3) are comparable to or shorter than those of the corresponding arsenic derivatives (Tables 2 and 3). A molecular‐orbital calculation performed on the model compounds (MeC(E)E^1^)~3−x~MMe~x~ (M = As, Sb, Bi; E = O, S; E^1^ = S, Se; x = 1, 2) at the RHF/LANL2DZ level supported this shortening of CE ⋅⋅⋅ Sb distances (Table 4). Natural‐bond‐orbital (NBO) analyses of the model compounds also revealed that two types of orbital interactions n~S~ → σ$\rm{_{{{MC}}}^\ast }$ and n~S~ → σ$\rm{_{{{MS(1)}}}^\ast }$ play a role in the (thioacyl)thio derivatives (MeCSS)~3−x~MMe~x~ (x = 1, 2) (Table 5). In the acylthio‐MeCOSMMe~2~ (M = As, Sb, Bi), n~O~ → σ$\rm{_{{{MC}}}^\ast }$ contributes predominantly to the orbital interactions, but in MeCOSeSbMe~2~, none of n~O~ → σ$\rm{_{{{MC}}}^\ast }$ and n~O~ → σ$\rm{_{{{MSe}}}^\ast }$ contributes to the orbital interactions. The n~S~ → σ$\rm{_{{{MC}}}^\ast }$ and n~S~ → σ$\rm{_{{{MS(1)}}}^\ast }$ orbital interactions in the (thioacyl)thio derivatives are greater than those of n~O~ → σ$\rm{_{{{MC}}}^\ast }$ and n~O~ → σ$\rm{_{{{ME}}}^\ast }$ in the acylthio and acylseleno derivatives (MeCOE)~3−x~MMe~x~ (E = S, Se; M = As, Sb, Bi; x = 1, 2).
▪The reactions of RCOSeSbPh~2~ (R = 4‐MeC~6~H~4~) with piperidine led to the formation of piperidinium diphenylselenoxoantimonate(1−) (= piperidinium diphenylstibinoselenoite) (H~2~NC~5~H~10~)^+^Ph~2~SbSe^−^, along with the corresponding N‐acylpiperidine (Table 6). Similar reactions of the bis‐derivatives (RCOSe)~2~SbR^1^ (R, R^1^ = 4‐MeC~6~H~4~) with piperidine gave the novel di(piperidinium) phenyldiselenoxoantimonate(2−) (= di(piperidinium) phenylstibonodiselenoite), [(H~2~NC~5~H~10~)^+^]~2~(PhSbSe~2~)^2−^, in which the negative charges are delocalized on the SbSe~2~ moiety (Table 6). Treatment of RCOSeSbR$\rm{_2^1 }$ (R, R^1^ = 4‐MeC~6~H~4~) with N‐halosuccinimides indicated the formation of Se‐(halocyclohexyl) arenecarboselenoates (Table 8). Pyrolysis of bis(acylseleno)arylbismuth at 150° gave Se‐aryl carboselenoates in moderate to good yields (Table 9).