Dinuclear Pd(II) and Rh(I) complexes of tetra-acetylethane: Linkage isomerization of tetra-acetylethane dianion in Pd(II) complexes |
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| Affiliation: | 1. Tokyo University of Science, Departent of Civil Engineering, 2641 Yamazaki, Noda, 278-8510, Japan;2. Nagoya University, Graduate School of Environmental Studies, Furo-cho, Chikusa-ku, Nagoya, 464-8603, Japan |
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| Abstract: | The Pd(II) and Rh(I) complexes of tetra-acetylethane [H2dahd (3,4-diacetyl-2,4-hexadiene-2,5-diol)] with O,O′-bonded chelates, represented as [M2(O2,O′2-dahd)(L2)2][X]m {M = Pd, L2 = (PPh3)2 or bdpe [1,2-bis(diphenylphosphino)ethane], X = BF4 or PF6, m = 2; M = Rh, L = Co, m = 0}, have recently been prepared. [Pd2(O2,O′2-dahd)-(PPh3)4][PF6]2 reacts with the potentially bidentate 1,10-phenanthroline (phen) to give the five-coordinate complex [Pd(PPh3)(phen)2][PF6]2 and [Pd(O1,O′1-dahd)(phen)]n, the latter of which is rather insoluble in organic solvents. [Pd(O1, O′1-dahd)(phen)]n in CH2Cl2 readily transforms to a monomer complex [Pd(C3, O′-dahd)phen)]. These anomalous Pd(II) and Rh(I) complexes of the tetra-acetylethane dianion have been characterized from elemental analyses, conductance, IR, 1H and 13C NMR spectroscopy, magnetic susceptibility and ESR spectroscopy. |
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