European Journal of Inorganic Chemistry p. 120 - 127 (2003)
Update date:2022-08-05
Topics:
Elsegood, Mark R. J.
Holmes, Kathryn E.
Kelly, Paul F.
MacLean, Elizabeth J.
Parr, Jonathon
Stonehouse, Julia M.
Reaction of [PPh4]2[Pd2X6] (where X = Cl, Br or I) with 1,4-(PhS{NH})2C6H4 (1) in dichloromethane results in the formation of [Pd{1,4-(PhS{NH})2C6H4}X2] 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 [PdCl2(PhCN)2] with 1,2-(PhS{NH})-(PhS)C6H4 (3) results in the formation of [PdCl2{1,2-(PhS{NH})(PhS)C6H4}] (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 PPh3, generating trans-[PdCl2{1,2-(PhS{NH})(PhS)C6H4} PPh3] (5); further reaction with PPh3 results in complete removal of 3 from the system and formation of trans-[PdCl2(PPh3)2]. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
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