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.