Synthesis and Structure of Polymeric Networks of Silver Hexafluoroacetylacetonate Complexes of THF, Toluene, and Vinyltrimethylsilane

The reaction of 1,1,1,5,5,5-hexafluoroacetylacetone (Hhfac) with Ag₂O in the presence of L = THF, toluene, and Me₃SiCHCH₂ was studied to obtain [Ag(hfac)L]_x complexes for use as chemical vapor deposition precursors. The structures and volatilities of these three complexes were compared to those of the previously synthesized Ag(hfac)(Me₃SiC≡CSiMe₃), 1, which was also crystallographically characterized for comparison. The reaction of Ag₂O with Hhfac in THF forms the polymeric complex [Ag₄(hfac)₄(THF)₂]_∞, 2, which has tetrametallic subunits with hfac ligands that bridge via oxygen and carbon. Both 4- and 5-coordinate silver metal centers are found in 2. Ag₂O reacts with Hhfac in toluene to form a complex with a similar tetrametallic unit [Ag₄(hfac)₄(toluene)₂]_∞, 3. In this case, the tetrametallic subunits are assembled via bridging toluene molecules, and each silver is 6-coordinate. In the presence of excess vinyltrimethylsilane (vtms), Ag₂O and Hhfac form [Ag₃(hfac)₃(vtms)]_∞, 4, which contains trimetallic subunits assembled via oxygen atoms of bridging hfac ligands and 5- and 6-coordinate silver.