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Oxidative Addition of Diphenyldichalcogenides PhEEPh (E = S, Se, Te) to Low-Valent CN- and NCN-Chelated Organoantimony and Organobismuth Compounds
Authors: Šimon Petr | Jambor Roman | Růžička Aleš | Dostál Libor
Year: 2013
Type of publication: článek v odborném periodiku
Name of source: Organometallics
Publisher name: American Chemical Society
Place: Washington
Page from-to: 239-248
Titles:
Language Name Abstract Keywords
cze Oxidativní adice PhEEPh (E = S, Se, Te) na nízkovalentní CN- a NCN-Chelatované Organoantimonité a Organobismutité sloučeniny Reakcee (L4Sb4)-Sb-1 (1) (L-1 = [o-C6H4(CH=NC6H3(i-Pr)(2)-2,6)]) s difenyldichalkogenidy PhEEPh (E = S, Se, or Te) vedla k izolaci sloučenin (LSb)-Sb-1(EPh)(2) (E = S (2), Se (3), Te (4)). Analogicky reakce in situ připraveného organobismutitého prekurzoru vedla k přípravě diorganobismutité sloučeniny (L2Bi)-Bi-1(EPh) (E = S (6), Se (7), Te (8)). Oxidativní adice; nízkovalentní Organoantimonité a Organobismutité sloučeniny; CN- a NCN-Chelatované ligandy
eng Oxidative Addition of Diphenyldichalcogenides PhEEPh (E = S, Se, Te) to Low-Valent CN- and NCN-Chelated Organoantimony and Organobismuth Compounds The reactions of the organoantimony(I) compound (L4Sb4)-Sb-1 (1) (where L-1 = [o-C6H4(CH=NC6H3(i-Pr)(2)-2,6)]) with diphenyldichalcogenides PhEEPh (E = S, Se, or Te) gave compounds (LSb)-Sb-1(EPh)(2) (E = S (2), Se (3), Te (4)) as the result of the oxidative addition of the antimony(I) atom across the chalcogen-chalcogen bond. The reaction of diphenyldichalcogenides PhEEPh with an in situ prepared organobismuth(I) compound (via reaction of the parent chloride (LBiCl2)-Bi-1 (5) with two equivalents of K[B(s-Bu)(3)H]) gave surprisingly diorganobismuth compounds (L2Bi)-Bi-1(EPh) (E = S (6), Se (7), Te (8)) as the major products along with only a trace amount of the intended compounds (LBi)-Bi-1(EPh)(2) (E = S (9), Se (10), Te (11)). It turned out that this is the result of instability of 9-11 in solution, and their decomposition provided compounds 6-8. The bismuth compounds containing the pincer-type ligand L-2 (L-2 = [o,o-C6H3(CH2NMe2)(2)]) containing an extra donor pendant arm were studied with the aim to support their stability by an additional N -> Bi interaction. Thus, in situ preparation of the organobismuth(I) compound from (LBiCl2)-Bi-2 (12) and two equivalents of K[B(s-Bu)(3)H] followed by the addition of PhEEPh gave compounds (LBi)-Bi-2(EPh)(2) (E = S (13), Se (14), Te (15)). Compounds 13-15 showed no tendency for redistribution reaction, contrary to 9-11, due to the rigid coordination of both nitrogen donor atoms of the ligand L-2 to the bismuth atom. All studied compounds were characterized by the help of H-1 and C-13 NMR spectroscopy, by elemental analysis, and except compounds 4, 14, and 15 by single-crystal X-ray diffraction analyses. main-group elements; bond covalent radii; crystal-structures; solid-state; single-bond; complexes

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