Ketonyl complexes

The pivalamidate-bridged diplatinum ketonyl complexes may be prepared from the reaction of platinum blue complex and nitric acid in acetone. Two isomers with the amidate configuration in head-to-head and head-to-tail modes and the ketonyl ligand at one axial end are characterized (Scheme 16). An alternative route is from catalyzed oxidation of olefins. ... 

Under less acidic conditions, the reaction of 447 with HC CPh and the subsequent hydration follows a Markovnikov-type protocol resulting, at pH 4.0, in the a-ketonyl complex [Cp Ir(bpy)(CH2COPh)] 450. Hydrolysis of 450 occurs at pH 1.0 producing acetophenone in quantitative yield without any isomerization to the acyl species. 

C-H activation has been extended to a number of other methyl ketones MeC(0)R64 and the reactivity of ketonyl gold complexes has been explored in some... 

A series of alkynyl complexes TpRu(C=CR)Cl(NO) were prepared by Onishi et al. from TpRuCl2(NO) and an excess of terminal alkynes in the presence of NEts (Scheme 21)."° If the same reaction is performed with ethynylbenzene in the presence of Cul as catalyst, the novel bis(alkynyl) complex TpRu(C=CPh)2(NO) was obtained. " Upon treatment of these cr-acetylide complexes with one equivalent of H2O in the presence of HBF4 Et20 in distilled MeOH several compounds were obtained in good yields including ketonyl, bisketonyl, acyl and metallacyclopente-none complexes. 

Ogo S, Uehara K, Abura T, Watanabe Y, Fukuzumi S (2004) pH-Selective synthesis and structures of alkynyl, acyl, and ketonyl intermediates in anti-Markovnikov and Markovnikov hydrations of a terminal alkyne with a water-soluble iridium aqua complex in water. J Am ChemSoc 126 16520-16527... 

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