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Synthesis, solid state structure and spectro-electrochemistry of ferrocene-ethynyl phosphine and phosphine oxide transition metal complexes

Synthesis, solid state structure and spectro-electrochemistry of ferrocene-ethynyl phosphine and phosphine oxide transition metal complexes

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JAKOB, Alexander, Petra ECORCHARD, Michael LINSEIS, Rainer WINTER, Heinrich LANG, 2009. Synthesis, solid state structure and spectro-electrochemistry of ferrocene-ethynyl phosphine and phosphine oxide transition metal complexes. In: Journal of Organometallic Chemistry. 694(5), pp. 655-666. ISSN 0022-328X

@article{Jakob2009Synth-13796, title={Synthesis, solid state structure and spectro-electrochemistry of ferrocene-ethynyl phosphine and phosphine oxide transition metal complexes}, year={2009}, doi={10.1016/j.jorganchem.2008.11.046}, number={5}, volume={694}, issn={0022-328X}, journal={Journal of Organometallic Chemistry}, pages={655--666}, author={Jakob, Alexander and Ecorchard, Petra and Linseis, Michael and Winter, Rainer and Lang, Heinrich} }

Lang, Heinrich Synthesis, solid state structure and spectro-electrochemistry of ferrocene-ethynyl phosphine and phosphine oxide transition metal complexes eng 2011-06-22T07:19:51Z 2009 Winter, Rainer Lang, Heinrich Ecorchard, Petra Jakob, Alexander First publ. in: Journal of Organometallic Chemistry 694 (2009),5, pp. 655-666 Linseis, Michael Ecorchard, Petra 2011-06-22T07:19:51Z Winter, Rainer The synthesis of ferrocene-ethynyl phosphine platinum dichloride complexes based on (FcCtriple bond; length of mdashC)nPh3−nP (1a, n = 1; 1b, n = 2; 1c, n = 3; Fc = ferrocenyl, (η5-C5H5)(η5-C5H4)Fe) is described. Air-oxidation of 1c afforded (FcCtriple bond; length of mdashC)3Pdouble bond; length as m-dashO (6). Treatment of 1a–1c with [(PhCtriple bond; length of mdashN)2PtCl2] (2) or [(tht)AuCl] (tht = tetrahydrothiophene) (7), respectively, gave the heterometallic transition complexes cis-[((FcCtriple bond; length of mdashC)nPh3−nP)2PtCl2] (3a, n = 1; 3b, n = 2; 3c, n = 3) or [((FcCtriple bond; length of mdashC)nPPh3−n)AuCl] (8a, n = 1; 8b, n = 2). Further treatment of these molecules with HCtriple bond; length of mdashCMc (4a, Mc = Fc; 4b, Mc = Rc = (η5-C5H5)(η5-C5H4)Ru) in the presence of [CuI] produced trans-[((FcCtriple bond; length of mdashC)Ph2P)2Pt(Ctriple bond; length of mdashCFc)2] (5) (reaction of 3a with 4a) and [(FcCtriple bond; length of mdashC)nPh3−nPAuCtriple bond; length of mdashCMc] (n = 1: 9a, Mc = Fc; 9b, Mc = Rc; n = 2: 11a, Mc = Fc; 11b, Mc = Rc) (reaction of 4a, 4b with 8a, 8b), respectively.<br />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.<br />The electrochemical and spectro-electrochemical behavior of complexes 5, 8a, 9a, 9b and [(Ph3P)AuCtriple bond; length of mdashCFc] was investigated in the UV/Vis/NIR. Near IR bands that are likely associated with charge transfer from the ((FcCtriple bond; length of mdashC)Ph2P)2Pt or the ((FcCtriple bond; length of mdashC)nPh3−nP)Au (n = 0, 1) moieties appear upon oxidation of the σ-bonded ferrocene-ethynyl groups. These bands undergo a (stepwise) blue shift as ferrocene-ethynyl substituents on the phosphine coligands are oxidized. deposit-license Jakob, Alexander Linseis, Michael

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