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• W1975804946 abstract "Die Synthese der zweifach positiv geladenen Tris(trialkylphosphit)-Komplexe [C5H5Co{P(OC2H5)3}3]2+ (2a) und [C5H5Co{P(OCH3)3}3]2+ (2b) wird beschrieben. 2b und [C5(CH3)5Rh{P(OCH3)3}3]2+ (5) reagieren mit Iodid und Cyanid in einer Sequenz von drei Michaelis-Arbusov-artigen Reaktionen zu den Titelkomplexen L− = [C5R5M{P(O)(OCH3)2}3]−, R = CH3, H, M = Rh, Co (1b, 8) unter Abspaltung von 3 mol CH3I bzw. CH3CN. Die anionischen Komplexe L− verhalten sich gegenüber Metall-Ionen Mn+ in wäßriger Lösung wie Sauerstoff-Tripodliganden. Es entstehen 2:1-Komplexe [ML2](n−2)+, Mn+ = Co2+, Ni2+, Cu2+, Cd2+, Mg2+, Bi3+ (10a–e,i,11a–e). Die spektroskopischen Daten sprechen in allen Fällen für eine oktaedrische Koordination des Metall-Ions Mn+ durch die 6 PO-Sauerstoffatome der beiden Liganden L−. Die Cyclopentadienyl-Komplexe [(C5H5)3Ni2]+ reagieren mit L− rasch zu NiL2 (9b, 10b) bzw. FeL2 (9f, 10f). Im Gegensatz dazu führt die Umsetzung von L− mit [{C5(CH3)5RhCl2}2] und [{Aromat)RuCl2}2] zu kationischen zweikernigen Sandwich-Komplexen des Typs [(Ring)M{P(O)R2}3M′(Ring′)]+, Ring = C5H5, C5(CH3)5, M = Co, Rh, R = OCH3, OC2H5, M′ = Rh, Ru, Ring′ = C5(CH3)5, C6H6, p-Cymol (z. B. 12, 13). L− = [C5H5Co{P(O)(OC2H5)2}3]− ergibt mit (PPh3)2CuNO3 den Kupfer(I)-Komplex LCuPPh3 (14). Die Elektronenspektren der 3d-Übergangsmetallkomplexe ML2 zeigen, daß die ligandfeldspektroskopischen Eigenschaften von L− = [C5R5M{P(O)R′2}3]−, R = H, CH3, M = Co, Rh, R′ = OCH3, OC2H5, praktisch unabhängig von R, M und R′ sind. Es sind alles schwache und unerwartet harte Liganden. Sie stehen in der nephelauxetischen Reihe bei DMSO und Wasser. Ihre Ligandfeldstärke entspricht etwa der des Fluorid-Ions. Synthesis of New Oxygen Tripod Ligands of the Type [C5R5M{P(O)(OCH3)2}3]− via the Michaelis-Arbusov Reaction. Their Ligand Field Properties and their Coordination Chemistry The synthesis of the dicationic tris(trialkylphosphite) complexes [C5H5Co{P(OC2H5)3}3]2+ (2a) and [C5H5Co{P(OCH3)3}3]2+ (2b) is described. 2b and [C5(CH3)5Rh{P(OCH3)3}3]2+ (5) react with iodide or cyanide in a sequence of three Michaelis-Arbusov reactions to give the title complexes L− = [C5R5M{P(O)(OCH3)2}3]−, R = CH3, H, M = Rh, Co (1b, 8), and 3 mol CH3I or CH3CN. The anionic complexes L− react as oxygen tripod ligands with metal ions Mn+ in aqueous solutions to form 2:1 complexes [ML2](n−2)+, Mn+ = Co2+, Ni2+, Cu2+, Cd2+, Mg2+, Bi3+ (10a–e, i, 11a–e). In all cases the metal ions Mn+ can be postulated to be octahedrally coordinated by the 6 P = O oxygen atoms of the two ligands L−. The cyclopentadienyl complexes [(C5H5)3Ni2]+ and [C5H5Fe(CO)2H2O]+ react readily with L− to yield NiL2 (9b, 10b) and FeL2 (9f, 10f) whereas [{C5(CH3)5RhCl2}2] and [{arene RuCl2}2] form cationic dinuclear sandwich complexes of the type [(ring)M{P(O)R2}3M′(ring′)]+, ring = C5H5, C5(CH3)5, M = Co, Rh, R = OCH3, OC2H5, M′ = Rh, Ru, ring′ = C5(CH3)5, C6H6, p-cymene (e.g. 12, 13). (PPh3)2CuNo3 reacts with L− = [C5H5Co{P(O)(OC2H5)2}3] − to give the copper(I) complex LCuPPh3 (14). The electronic spectra of the 3d transition metal complexes ML2 indicate that the ligand field properties of L− = [C5R5M{P(O)R2′}3]−, R = H, CH3, M = Co, Rh, R′ = OCH3, OC2H5, are nearly independent of R, M, and R′. They are all weak and unexpectedly hard ligands. Their position in the nephelauxetic series in near DMSO and water. The ligand field strength is comparable to the one of fluoride." @default.
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• W1975804946 date "1982-05-01" @default.
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• W1975804946 title "Die Michaelis‐Arbusov‐Reaktion als Zugang zu neuen Sauerstoff‐Tripodliganden des Typs [C ₅ R ₅ M{P(O)(OCH ₃ ) ₂ } ₃ ] ⁻ . Ligandfeldspektroskopische und koordinationschemische Charakterisierung der Liganden" @default.
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• W1975804946 doi "https://doi.org/10.1002/cber.19821150522" @default.
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