Reactions of Gold(III) Oxo Complexes with PPh3 and Alkenes. Crystal Structure of [Au(bipyip)(n 2-CH2=CHPh)][PF6] (bipyip = 6-iso-propyl-2,2?-bipyridine).

Some aspects of the reactivity of the two different kinds of gold(III) oxo complexes [Au2(N,N)2(?-O)2][X]2 [N,N = 2,2'-bipyridine (bipy) (1), 6-alkyl-2,2'-bipyridine (bipyR) (2), R = Me a, CH2Me b, CHMe2 c, CMe3 d, CH2CMe3 e] and [Au2(C,N,N)2(?-O)][X]2 [HC,N,N = 6-benzyl-2,2'-bipyridine (bipyR') (3), R' = CHMeC6H5 a, CMe2C6H5 b] (X = BF4, PF6) have been studied. Treatment with water converts the unsubstituted bipyridine complex [Au2(bipy)2(?-O)2][PF6]2 (1) and the cyclometallated derivatives [Au2(C,N,N)2(?-O)][PF6]2 (3) into the water soluble monomeric hydroxo species [Au(bipy)(OH)2][PF6] (4) and [Au(C,N,N)(OH)][PF6] (5), respectively. These hydroxo species, likely the intermediates in the formation of the oxo complexes, are quantitatively reverted to the latter ones by reflux in anhydrous solvents. Both kinds of oxo complexes react with PPh3 to give OPPh3, the gold(I) complex [Au(PPh3)2][PF6] and the free bipyridine ligands. The reaction of the dioxo complexes [Au2(bipyR)2(?-O)2][PF6]2 (2a, 2b, 2c, 2e) with different alkenes gives the unprecedented alkene complexes [Au(bipyR)(?2-alkene)][PF6]. The styrene adduct [Au(bipyip)(?2- CH2=CHPh)][PF6] (7) (bipyip = 6-iso-propyl-2,2?-bipyridine c) has been characterized, inter alia, by X-ray diffraction analysis. Organic products arising from olefin oxidation are also found in the reaction mixture.