Oxidative addition of a hypervalent transannular sulfur-sulfur bond to a Pd(0) complex: Synthesis and crystal structures of 1,5- dithiacyclooctanepalladium(II) bis(trifluoromethanesulfonate) having phosphine ligands

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A hypervalent compound 1,5-bis(trifluoromethylsulfonyloxy)-lλ4,5λ4- dithiabicyclo[3.3.0]octane (1) oxidatively reacted with Pd2(dba)3 (dba = dibenzylidene acetone) in acetonitrile to give a dicationic complex [Pd(dtco)(CH3CN)2]-(OTf)2 (2) (DTCO = 1,5-dithiacyclooctane), in which the DTCO ligand coordinated in cis-chelation to the palladium metal. Acetonitrile in 2 was labile enough to be readily replaced by phosphine ligands to give dicationic DTCO-phosphine palladium complexes of the formula [Pd(dtco)(L)2](OTf)2 (3: L = PMe2Ph; 4: L = PPh3; 5: L2 = 1,2- bis(diphenylphosphino)ethane; 6: L2 = (R)-2,2'-bis(diphenylphosphino)- 1,1'- binaphthyl). Molecular structures of 5 and 6 have been characterized by X- ray analysis, indicating that each of these two complexes consists of a discrete dicationic palladium(II) species [Pd(dtco)L2]2+ and two trifluoromethanesulfonate ions without any cation-anion bonding interaction, and revealing that the DTCO is coordinated to the palladium center as a bidentate ligand and that two phosphorus atoms ultimately coordinated to the metal in cis-fashion.

Original languageEnglish
Pages (from-to)2859-2864
Number of pages6
JournalBulletin of the Chemical Society of Japan
Issue number12
Publication statusPublished - 1998
Externally publishedYes


ASJC Scopus subject areas

  • Chemistry(all)

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