Zusammenfassung
The synthesis of ferrocene-ethynyl phosphine platinum dichloride complexes based on (FcC C)(n)Ph-3 P-n (1a, n = 1; 1b, n = 2; 1c, n = 3; Fc = ferrocenyl, (eta(5)-C5H5)(eta(5)-C5H4)Fe) is described. Air-oxidation of 1c afforded (FcC C)(3)P=O (6). Treatment of 1a-1c with [(PhC N)(2)PtCl2] (2) or [(tht)AuCl] (tht = tetrahydrothiophene) (7), respectively, gave the heterometallic transition complexes ...
Zusammenfassung
The synthesis of ferrocene-ethynyl phosphine platinum dichloride complexes based on (FcC C)(n)Ph-3 P-n (1a, n = 1; 1b, n = 2; 1c, n = 3; Fc = ferrocenyl, (eta(5)-C5H5)(eta(5)-C5H4)Fe) is described. Air-oxidation of 1c afforded (FcC C)(3)P=O (6). Treatment of 1a-1c with [(PhC N)(2)PtCl2] (2) or [(tht)AuCl] (tht = tetrahydrothiophene) (7), respectively, gave the heterometallic transition complexes cis-[((FcC C)(n) Ph-3 P-n)(2)PtCl2] (3a, n = 1; 3b, n = 2; 3c, n = 3) or [((FcC C)(n)PPh3 (n))AuCl] (8a, n = 1; 8b, n = 2). Further treatment of these molecules with HC CMc (4a, Mc = Fc; 4b, Mc = Rc = (eta(5)-C5H5)(eta(5)-C5H4)Ru) in the presence of [CuI] produced trans-[((FcC C)Ph2P)(2)Pt(C CFc)(2)] (5) (reaction of 3a with 4a) and [(FcC C)(n)Ph-3 nPAuC CMc] (n = 1: 9a, Mc = Fc; 9b, Mc = Rc; n = 2: 11a, Mc = Fc; 11b, Mc = Rc) (reaction of 4a, 4b with 8a, 8b), respectively. The structures of 3a, 5, 6, 8, 9a, and 9b in the solid state were established by single-crystal X-ray structure analysis. The main characteristic features of these molecules are the linear phosphorus-gold-acetylide arrangements, the tetra-coordination at phosphorus and the square-planar surrounding at platinum. The electrochemical and spectro-electrochemical behavior of complexes 5, 8a, 9a, 9b and [(Ph3P)AuC CFc] was investigated in the UV/Vis/NIR. Near IR bands that are likely associated with charge transfer from the ((FcC C)Ph2P)(2)Pt or the ((FcC C)(n)Ph-3 P-n)Au (n = 0, 1) moieties appear upon oxidation of the sigma-bonded ferrocene-ethynyl groups. These bands undergo a (stepwise) blue shift as ferrocene-ethynyl substituents on the phosphine coligands are oxidized. (C) 2008 Elsevier B.V. All rights reserved.
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