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Reactions of Bis(dibenzobarrelenyl) Dichalcogenides with a Palladium(0) Complex: Unexpected Formations of Mononuclear Chalcogenide(dichalcogenolato)palladium(II) Complexes and Dichalcogenahexacyclo Compounds
Author(s) -
Nakata Norio,
Yamaguchi Yuki,
Ishii Akihiko
Publication year - 2014
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201402518
Subject(s) - chemistry , palladium , chalcogenide , toluene , sulfur , ligand (biochemistry) , sulfide , chelation , medicinal chemistry , stereochemistry , inorganic chemistry , organic chemistry , catalysis , biochemistry , receptor
Abstract Thermal reactions of bis(dibenzobarrelenyl) dichalcogenides [(DbbS) 2 and (DbbSe) 2 ] with [Pd(PPh 3 ) 4 ] in toluene afforded novel mononuclear chalcogenide(dichalcogenolato)Pd II complexes [Pd(EDbb‐12‐EDbb)(EDbb)(PPh 3 )] (E = S, Se) together with dichalcogenahexacyclo compounds. The reaction in the presence of PPh 3 in toluene at 110 °C led to a cyclometalation to furnish the corresponding four‐membered 1,2‐chalcogenapalladacycles [Pd(EDbb)(PPh 3 ) 2 ] (E = S, Se) with dichalcogenahexacyclo compounds. The structures of these Pd II complexes and cyclization products were fully characterized on the basis of their NMR spectroscopic data and X‐ray analyses. In the crystalline state of [Pd(SDbb‐12‐SDbb)(SDbb)(PPh 3 )], two thiolato sulfur atoms occupy cis positions with respect to the PPh 3 , and the sulfide sulfur atom from the chelating sulfido(thiolato) ligand is situated at the trans position.