This paper describes the solution chemistry of the species (hfac)Ag(SEt(2)) and Pd(hfac)(2) which have been used as metal-organic precursors for the aerosol-assisted (AA) chemical vapor deposition (CVD) of Ag1-xPdx alloy films. The reaction between (hfac)Ag(SEt(2)) and Pd(hfac)(2) was investigated in toluene solution and found to result in a reaction with formation of the species Pd(hfac-C)(hfac-O,O)(SEt(2)) and [(hfac)Ag](4)(SEt(2)). These two species were characterized in solution by NMR spectroscopy and in the solid state by FTIR, elemental analysis, and single-crystal X-ray diffraction. The solid state structure of Pd(hfac-C)(hfac-O,O)(SEt(2)) confirmed the monomeric square planar four-coordinate structure of this molecule with two different hfac bonding modes. Crystal data : empirical formula C14H12PdF12O4S : crystal system monoclinic; space group P2(1)/n; unit cell dimensions a = 9.0273(9) (2), b = 26.248(3), c = 9.763(8) Angstrom; beta = 103.042(2)degrees; Z = 4. The species [(hfac)Ag](4)(SEt(2)), comprised "(hfacAg)(4)" tetramers connected by bridging SEt(2) groups to forman infinite polymer. This structure is remarkable for the presence of unusual unsupported mu-SEt(2) and mu(4)-hfac ligand binding modes. Crystal data : empirical formula C24H14Ag4F24O8S; crystal system monoclinic; space group C2/c; unit cell dimensions a = 24.776(2), b = 9.5179(8), c = 19.940(3) Angstrom; beta = 126.724(8)degrees; Z = 4. The observation of this unusual coordination mode for mu-SEt(2) prompted us to structurally characterize (hfac)Ag(SEt(2)) in the solid state by single-crystal X-ray diffraction. Crystal data : empirical formula C9H11AgF6O2S; crystal system hexagonal; space group P6(1)22; unit cell dimensions a = 10.853(4), c = 18.850(1) Angstrom; Z = 6. This compound is monomeric in the solid state with a unidentate SEt(2) ligand.