Jakob, Alexander and Ecorchard, Petra and Linseis, Michael and Winter, Rainer F. and Lang, Heinrich (2009) Synthesis, solid state structure and spectro-electrochemistry of ferrocene-ethynyl phosphine and phosphine oxide transition metal complexes. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 694 (5). pp. 655-666. ISSN 0022-328X, 1872-8561
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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.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | RUTHENIUM(II) TERPYRIDINE COMPLEXES; MIXED-VALENCE COMPLEXES; RICH BRIDGING UNITS; CRYSTAL-STRUCTURE; MOLECULAR WIRES; FERROCENYLACETYLIDE COMPLEXES; ELECTROCHEMICAL-BEHAVIOR; COORDINATION CHEMISTRY; PLATINUM(II) COMPLEXES; ACETYLIDE COMPLEXES; Ferrocene; Phosphine alkynyls; Heteromultimetallic; Spectro-electrochemistry |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Alumni or Retired Professors > Arbeitskreis Prof. Dr. Rainer Winter |
| Depositing User: | Petra Gürster |
| Date Deposited: | 27 Oct 2022 08:52 |
| Last Modified: | 27 Oct 2022 08:52 |
| URI: | https://pred.uni-regensburg.de/id/eprint/29393 |
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