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 triple bond 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]infinity, 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]infinity, 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)]infinity, 4, which contains trimetallic subunits assembled via oxygen atoms of bridging hfac ligands and 5- and 6-coordinate silver.