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) |
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Authors: | Mitsutoshi Kimura Akiyuki Iwata Masahiro Itoh Kazuki Yamada Tsutomu Kimura Noriyuki Sugiura Masaru Ishida Shinzi Kato |
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Abstract: | A series of (thioacyl)thio]‐ and (acylseleno)antimony and (thioacyl)thio]‐ and (acylseleno)bismuth, i.e., (RCSS)xMR and (RCOSe)xMR (M = Sb, Bi, R1 = 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‐MeC6H4CSS)2Sb(4‐MeC6H4) ( 9b′ ), (4‐MeOC6H4COSe)2Sb(4‐MeC6H4) ( 12c′ ), (4‐MeOC6H4COS)2Bi(4‐MeC6H4) ( 15c′ ), and (4‐MeOC6H4CSS)2BiPh ( 18c ) along with (4‐MeC6H4COS)2SbPh ( 6b ) and (4‐MeC6H4COS)3Sb ( 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 C?S ??? Sb distances in (RCSS)2MR1 (M = As, Sb, Bi; R1 = aryl) and the C?O ??? Sb distances in (RCOS)xMR (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)E1)3?xMMex (M = As, Sb, Bi; E = O, S; E1 = S, Se; x = 1, 2) at the RHF/LANL2DZ level supported this shortening of C?E ??? Sb distances (Table 4). Natural‐bond‐orbital (NBO) analyses of the model compounds also revealed that two types of orbital interactions nS → σ and nS → σ play a role in the (thioacyl)thio derivatives (MeCSS)3?xMMex (x = 1, 2) (Table 5). In the acylthio‐MeCOSMMe2 (M = As, Sb, Bi), nO → σ contributes predominantly to the orbital interactions, but in MeCOSeSbMe2, none of nO → σ and nO → σ contributes to the orbital interactions. The nS → σ and nS → σ orbital interactions in the (thioacyl)thio derivatives are greater than those of nO → σ and nO → σ in the acylthio and acylseleno derivatives (MeCOE)3?xMMex (E = S, Se; M = As, Sb, Bi; x = 1, 2). ?The reactions of RCOSeSbPh2 (R = 4‐MeC6H4) with piperidine led to the formation of piperidinium diphenylselenoxoantimonate(1?) (= piperidinium diphenylstibinoselenoite) (H2NC5H10)+Ph2SbSe?, along with the corresponding N‐acylpiperidine (Table 6). Similar reactions of the bis‐derivatives (RCOSe)2SbR1 (R, R1 = 4‐MeC6H4) with piperidine gave the novel di(piperidinium) phenyldiselenoxoantimonate(2?) (= di(piperidinium) phenylstibonodiselenoite), (H2NC5H10)+]2(PhSbSe2)2?, in which the negative charges are delocalized on the SbSe2 moiety (Table 6). Treatment of RCOSeSbR (R, R1 = 4‐MeC6H4) 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). |
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Keywords: | Carbodithioatoantimony Carboselenoatobismuth Chalcogenocarboxylate Pyrolysis Carboselenoatoantimony |
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