- ETHYNYLATION REACTIONS USING THE BIS(PHENYLETHYNYL)CUPRATE(I) COMPLEX ANION. PREPARATION OF THE BIS(PHENYLETHYNYL)AURATE(I) COMPLEX ANION
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Four new routes are described for the preparation of the linear diorganoaurate(I) complex -.These are based on the reactions of the analogous copper(I) complex anion - with , ,
- Abu-Salah, O.M.,Al-Ohaly, A.R.
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- Low-Nuclearity Alkynyl d10 Clusters Supported by Chelating Multidentate Phosphines
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The coordination chemistry of the tri- and tetradentate chelating phosphines (2-PPh2C6H4)2P(O)Ph (P3O) and (2-PPh2C6H4)3P (P4) with respect to d10 copper subgroup metal ions has been investigated. Depolymerization of (MC2R)n (M = Cu, Ag) with P4 affords the series of mono- and trinuclear complexes (P4)CuC2Ph (1), (P4)Cu3(C2Ph)3 (2), (P4)Ag3(C2Ph) (Hal)2 (Hal = Cl (3), Br (4), I (5)). Reactions of the M+ (M = Cu, Ag) ions with (M′C2R)n (M′ = Cu, Ag, Au) acetylides in the presence of P4 yield the family of dinuclear species [(P4)MM′(C2R)]+ (6-12), which comprise the Cu2/Ag2 (6, 7; R = Ph), AuCu (8-10; R = Ph, C(OH)Me2, C(OH)Ph2), and AuAg (11, 12; R = Ph, C(OH)Ph2) metal cores. A related triphosphine, (2-PPh2C6H4)2PPh (P3), applied in a similar protocol undergoes partial oxidation and leads to the heterotrimetallic clusters [{(P3O)M}2Au(C2R)2]+ (M = Cu, R = C(OH)Ph2, 13; M = Ag, R = C(OH)Ph2, 14; M = Ag, R = Ph, 15), which can be prepared more efficiently starting from the oxidized ligand P3O. The structures of the complexes 1-4 and 6-15 were established by single-crystal X-ray crystallography. According to the variable-temperature 1H and 31P{1H} NMR experiments, compounds 1-12 demonstrate fluxional behavior in solution. The title complexes do not show appreciable luminescence in solution at 298 K, and the photophysical properties of 1-15 were studied in the solid state. The observed phosphorescence (em up to 0.46, λem from 440 to 635 nm) is assigned to cluster-centered transitions mixed with some MLCT d →π?(alkynyl) character.
- Belyaev, Andrey,Dau, Thuy Minh,J?nis, Janne,Grachova, Elena V.,Tunik, Sergey P.,Koshevoy, Igor O.
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p. 3763 - 3774
(2016/11/22)
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