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 ]

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)