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 Ag ₂ O in the presence of L = THF, toluene, and Me ₃ SiCH=CH ₂ 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)(Me ₃ SiC≡CSiMe ₃ ), 1 , which was also crystallographically characterized for comparison. The reaction of Ag ₂ O with Hhfac in THF forms the polymeric complex [Ag ₄ (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 . Ag ₂ O reacts with Hhfac in toluene to form a complex with a similar tetrametallic unit [Ag ₄ (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), Ag ₂ O and Hhfac form [Ag ₃ (hfac) ₃ (vtms)] _∞ , 4 , which contains trimetallic subunits assembled via oxygen atoms of bridging hfac ligands and 5- and 6-coordinate silver.