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Fernandez D, Garcia-Seijo MI, Castineiras A, Garcia-Fernandez ME: Ring-opening reactions induced by gold (I) of five- and four-coordinate palladium (II) and platinum (II) complexes containing tripodal or linear polyphosphines. Dalton Trans. 2004 Aug 21;(16):2526-33. Epub 2004 Jul 22.
The tripodal ligands NP (3)(tris [2-(diphenylphosphino) ethyl] amine) and PP (3)(tris [2-(diphenylphosphino) ethyl] phosphine), form five-coordinate [Pd (NP (3)) X] X [X = Cl (1), Br (2)], [M (PP (3)) X] X [M = Pd: X = Cl (4), Br (5), I (6); M = Pt, X = Cl (7), Br (8), I (9)] and four-coordinate [Pd (NP (3)) I] I (3) complexes containing three fused rings around the metal. The interaction between Au (tdg) X (tdg = thiodiglycol; X = Cl, Br) or AuI and the respective ionic halo complexes 1-9 in a 1:1 stoichiometric ratio occurs via a ring-opening reaction with formation of the heterobimetallic systems PdAu (NP (3)) X (3)[X = Cl (11), Br (12), I (13)], [MAu (PP (3)) X (2)] X [M = Pd: X = Cl (14), Br (15), I (16); M = Pt: X = Cl (17), Br (18), I (19)]. The cations of complexes 17 and 18 were shown, by X-ray diffraction, to contain a distorted square-planar Pt (II) arrangement (Pt (P (2) P) X) where PP (3) is acting as tridentate chelating ligand and an almost linear PAuX moiety bearing the dangling phosphorus formed in the ring-opening process. PPh (3) coordinates to Au (I) and not to M (II) when added in excess to 14 and 17. Complexes 14-17 and [Pt (P (4))](BPh (4))(2) (10) (P4=linear tetraphosphine) also react with A (I), via chelate ring-openings to give MAu (2)(PP (3)) X (4) [M = Pd: X = Cl (20), Br (21), I (22); M = Pt: X = Cl (23)] and [Pt (2) Au (2)(mu-Cl)(2)(mu-P (4))(2)](BPh (4))(4) (24), respectively. |
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