Low-Nuclearity Alkynyl d10 Clusters Supported by Chelating Multidentate Phosphines

Abstract

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 structure...