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- W1566203218 abstract "The photo-induced substitution of a CO ligand has been used to prepare the halfsandwich complexes (η3-C3H5)V(CO)4[P(C7H7)3] (1), (η5-C5H5)V(CO)3[P(C7H7)3] (2), (η7-C7H7)V(CO)2[P(C7H7)3] (3), (η6-C6H3Me3)Cr(CO)2[P(C7H7)3] (4), and (η5-C5H5)Mn(CO)2[P(C7H7)3] (7), in which the olefinic phosphane is coordinated as a conventional two-electron ligand through the lone pair of electrons at phosphorus. Some analogues, which are permethylated at the aromatic ring (2*, 4*, 7*), were included for comparison. Subsequent photo-elimination of another CO group from 4 or 7 converts the olefinic phosphane into a chelating four-electron ligand, leading to (η6-C6H3Me3)Cr(CO)[P(C7H7)2(η2-C7H7)] (5) and (η5-C5H5)Mn(CO)[P(C7H7)2(η2-C7H7)] (8), respectively. The η2-coordinated double bond in 5 and 8 can be displaced by trimethylphosphite to give (η6-C6H3Me3)Cr(CO)[P(C7H7)3][P(OMe)3] (6) and (η5-C5H5)Mn(CO)[P(C7H7)3][P(OMe)3] (9). The 31P and 13C NMR spectra of all complexes are discussed, and X-ray structure analyses for 2 and 8 are presented. Prolonged irradiation of 7 and 8 led to a di(cycloheptatrienyl)phosphido-bridged dimer, {(η5-C5H5)Mn(CO)[P(C7H7)2]}2(10). Halbsandwich-Carbonylmetallkomplexe des Vanadiums, Chroms und Mangans mit Tri(1-cyclohepta-2, 4, 6-trienyl)phosphan, P(C7H7)3 Durch photo-induzierte Substitution eines CO-Liganden wurden die Halbsandwich-Komplexe (η3-C3H5)V(CO)4[P(C7H7)3] (1), (η5-C5H5)V(CO)3[P(C7H7)3] (2), (η7-C7H7)V(CO)2[P(C7H7)3] (3), (η6-C6H3Me3)Cr(CO)2[P(C7H7)3] (4) und (η5-C5H5)Mn(CO)2[P(C7H7)3] (7) dargestellt, in denen das olefinische Phosphan als konventioneller Zweielektronenligand über das freie Elektronenpaar am Phosphor koordiniert ist. Einige Analogkomplexe, die am aromatischen Ring permethyliert sind (2*, 4*, 7*), wurden zum Vergleich miteinbezogen. Nachfolgende Photo-eliminierung einer weiteren CO-Gruppe aus 4 oder 7 wandelt das olefinische Phosphan in einen Vierelektronen-Chelatliganden um, wobei (η6-C6H3Me3)Cr(CO)[P(C7H7)2(η2-C7H7)] (5) bzw. (η5-C5H5)Mn(CO)[P(C7H7)2(η2-C7H7)] (8) entstehen. Die η2-koordinierte Doppelbindung in 5 und 8 läßt sich durch Trimethylphosphit unter Bildung von (η6-C6H3Me3)Cr(CO)[P(C7H7)3][P(OMe)3] (6) und (η5-C5H5)Mn(CO)[P(C7H7)3][P(OMe)3] (9) verdrängen. Die 31P- und 13C-NMR-Spektren aller Komplexe werden diskutiert, und für 2 und 8 wurden Röntgenstrukturanalysen durchgeführt. Längerdauernde Bestrahlung von 7 und 8 führte zu einem di(cycloheptatrienyl)phosphido-verbrückten Dimeren, {(η5-C5H5)Mn(CO)[P(C7H7)2]}2 (10)." @default.
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- W1566203218 date "2002-01-01" @default.
- W1566203218 modified "2023-10-12" @default.
- W1566203218 doi "https://doi.org/10.1002/1521-3749(200213)628:13<2919::aid-zaac2919>3.0.co;2-7" @default.
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