Dinuclear Gold(I) "A-Frame" Complexes from Geminal Diauration of 2,4-Diketones, Methylenedisulfones, and Cyanomethyl Sulfones

Bratislav Djordjevic, Keith A. Porter, Stefan Nogai, Annette Schier, Hubert Schmidbaur

Research output: Contribution to journalArticlepeer-review

20 Scopus citations


Treatment of the disulfones RSO2CH2SO2R (R = Me, Ph) with 1 or 2 equiv of organolithium reagents, followed by metathesis with a (phosphine/arsine)gold(I) halide, afforded high yields of mono- or diaurated sulfones of the types [(R′3P)Au]CH(SO 2R)2 (R = R′ = Ph) and [(R′ 3P/As)Au]2{u-C(SO2R)2} (R = Me, R′3P = Ph3P, Ph2MeP, Ph3As; R = Ph, R′3P = PPh3, Ph2MeP). Using the same procedure, PhSO2CH2CN was transformed into [(Ph 3P)Au]2{u-C(CN)SO2Ph}. The products are stable to air and moisture and decompose at temperatures well above 150 °. The crystal structure analysis of the diaurated compounds reveals compact A-frame core units in which the central carbon atom forms a CAu2 triangle with an exceedingly small Au-C-Au angle and, consequently, a short aurophilic Au- - -Au contact. The corresponding angles S-C-S (or SAuC(N)) are widened in an overall distorted-tetrahedral environment. Attempted triauration using [(R′3P)Au]+BF4- reagents was unsuccessful with the disulfones but gave the adduct {[(Ph3P)Au] 2C(SO2Ph)CN[Au(PPh3)]}+BF 4-, in which the third gold atom is attached to the nitrile nitrogen atom. Benzyl phenyl sulfone was monoaurated to give the chiral product [(Ph3P)Au]CH(Ph)SO2Ph. 3-[(Triphenylphosphine)gold]pentane-2,4-dione was found to undergo a redistribution reaction induced by tritert-butoxyaluminum in benzene solution to give the diaurated diketone [(Ph3P)Au] 2{u-C{C(O)Me}2]. Its crystal structure shows a core unit with bonding characteristics similar to those of keto instead of sulfone/cyano substituents.

Original languageEnglish
Pages (from-to)5336-5344
Number of pages9
Issue number25
StatePublished - 8 Dec 2003
Externally publishedYes


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