ic034649r_si_002.txt (76.89 kB)

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

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posted on 08.11.2003 by William J. Evans, Dimitrios G. Giarikos, Daniel Josell, Joseph W. Ziller
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.