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Preparation of the First Complexes of Bidentate Sulfimides; the X‐ray Crystal Structures of [PdBr 2 {1,4‐(PhS{NH}) 2 C 6 H 4 }] 2 , [PdCl 2 {1,2‐(PhS{NH})(PhS)C 6 H 4 }] and trans ‐[PdCl 2 {1,2‐(PhS{NH})(PhS)C 6 H 4 }PPh 3 ]
Author(s) -
Elsegood Mark R. J.,
Holmes Kathryn E.,
Kelly Paul F.,
MacLean Elizabeth J.,
Parr Jonathon,
Stonehouse Julia M.
Publication year - 2003
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.200390012
Subject(s) - chemistry , denticity , dichloromethane , crystal structure , metallacycle , palladium , medicinal chemistry , ligand (biochemistry) , stereochemistry , crystallography , triphenylphosphine , methanol , x ray crystallography , catalysis , solvent , organic chemistry , diffraction , biochemistry , physics , receptor , optics
Abstract Reaction of [PPh 4 ] 2 [Pd 2 X 6 ] (where X = Cl, Br or I) with 1,4‐(PhS{NH}) 2 C 6 H 4 ( 1) in dichloromethane results in the formation of [Pd{1,4‐(PhS{NH}) 2 C 6 H 4 }X 2 ] 2 ( 2 ). X‐ray crystallography (performed using a synchrotron source) confirms that in the case where X = Br ( 2a ) both the bis‐sulfimides act as bridging ligands through N−Pd bonds producing an 18‐membered ring system linking the four sulfur atoms into an almost perfect square. Changing the reaction solvent to methanol/dichloromethane results in the formation of a polymeric material. Reaction of [PdCl 2 (PhCN) 2 ] with 1,2‐(PhS{NH})(PhS)C 6 H 4 ( 3 ) results in the formation of [PdCl 2 {1,2‐(PhS{NH})(PhS)C 6 H 4 }] ( 4 ) in which 3 acts as a bidentate ligand, bound by N−Pd and S−Pd bonds to form a unique MSCCSN metallacycle. The Pd−S bond is broken upon reaction with one equivalent of PPh 3 , generating trans ‐[PdCl 2 {1,2‐(PhS{NH})(PhS)C 6 H 4 }PPh 3 ] ( 5 ); further reaction with PPh 3 results in complete removal of 3 from the system and formation of trans ‐[PdCl 2 (PPh 3 ) 2 ]. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)