Reactions of Organogold I Complexes

Many organogold complexes are light sensitive, and it has proved advantageous to store them in the dark. Thus even a-silylmethyl complexes, which have been shown to be more stable in general than their purely organic counterparts, decompose to metallic gold under irradiation (173). 

Addition of CI2 to organogold(I) complexes has also been achieved by reaction with thallium(III) chloride [Eq. (47)] (13, 36, 180-182), the cis isomers being produced by this method. Reactions with X2 gave the trans isomers (179). 

Stepwise addition of halogens to the trimeric complex, [Au C(OMe)= NMe ]3 produced (155) three complexes Au3 C(OMe)=NMe 3X ] (n = 2,4,6) by consecutive oxidation of the three gold(I) centers. Binuclear gold(I) ylide complexes, however, underwent (56) consecutive oxidative addition of X2 to give formal gold(II) and finally gold(III) products [Eq. (49)]. Crystal structure (188) and spectroscopic (56. 189, 190) data have 

Organogold(I) complexes undergo a number of insertion reactions with unsaturated molecules, such as olefins, acetylenes, and sulfur dioxide. Insertion of carbon monoxide or carbon dioxide has not been achieved, although the reverse reaction has been observed with C02 (7/). 

It was suggested (196) that the C2F4 insertion reactions probably proceed by a radical mechanism, although the isolation of a 1 1 adduct from the reaction of (NC)2C=C(CN)2 with [AuMe(PPh3)] (197, 198) suggests that such an intermediate might be involved in the former reaction. 

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