Dimethyl gold complexes bonded to partially dehydroxylated MgO powder calcined at 673 K were synthesized by adsorption of Au(CH3)(2)(acac) (acac is C5H7O2) from n-pentane solution. The synthesis and subsequent decomposition of the complexes by treatment in He or H-2 were characterized with diffuse reflectance Fourier transform infrared (DRIFT), X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) spectroscopies. The XANES results identify Au(III) in the supported complexes, and the EXAFS and DRIFTS data indicate mononuclear dimethyl gold complexes as the predominant surface gold species, consistent with the lack of Au-Au contributions in the EXAFS spectrum and the presence of v(as)(CH3) and v(s)(CH3) bands in the IR spectrum. EXAFS data show that each complex is bonded to two oxygen atoms of the MgO surface at an Au-O distance of 2.16 angstrom. The DRIFT spectra show that reaction of Au(CH3)2(acac) with MgO at room temperature also formed Mg(acac)(2) and H(acac) species on the support. Treatment of the dimethyl gold complexes in He or H-2 at increasing temperatures varying from 373 to 573 K removed CH3 ligands and caused aggregation forming zerovalent gold nanoclusters of increasing size, ultimately with an average diameter of about 30 angstrom. Analysis of the gas-phase products during the genesis of the gold clusters indicated formation of CH4 (consistent with removal of CH3 groups) and CO2 at 473-573 K, associated with decomposition of the organic ligands derived from acac species. O-2 and CO2 were also formed in the decomposition of ubiquitous carbonates present on the surface of the MgO support.