DOE OSTI2018
In an effort to generate single-source precursors for the production of metal-siloxide (MSiO x ) materials, the tris(trimethylsilyl)silanol (H-SST or H-OSi(SiMe 3 ) 3 (1) ligand was reacted with a series of group 4 and 5 metal alkoxides. The group 4 products were crystallographically characterized as: [Ti(SST) 2 (OR) 2 ] (OR = OPr i (2), OBu t (3), ONep (4)); [Ti(SST) 3 (OBu n )] (5); [Zr(SST) 2 (OBu t ) 2 (py)] (6); [Zr(SST) 3 (OR)] (OR = OBu t (7), ONep, (8)); [Hf(SST) 2 (OBu t ) 2 ] (9); and [Hf(SST) 2 (ONep) 2 (py) n ] (n = 1 (10) , n = 2 (10a)) where OPr i = OCH(CH 3 ) 2 , OBu t = OC(CH 3 ) 3 , OBu n = O(CH 2 ) 3 CH 3 , ONep = OCH 2 C(CH 3 ) 3 , py = pyridine. The crystal structures revealed SST substituted: monomeric Ti species that adopted a tetrahedral (T-4) geometry; monomeric Zr compounds with coordination that varied from T-4 to trigonal bipyramidal (TBPY- 5); and monomeric Hf complexes isolated in a TBPY-5 geometry. For the group 5 species, the following derivatives were structurally identified as: [V(SST) 3 (py) 2 ] (11), [Nb(SST) 3 (OEt) 2 ] (12), [Nb(0)(SST) 3 (py)] (13), 2[H][(Nb(μ-0) 2 (SST)) 6 (μ 6 -0)] (14), [Nb 8 O 10 (OEt) 18 (SST) 2 •1/5Na 2 O] (15), [Ta(SST)([μ-OEt)(OEt) 3 ] 2 (16), and [Ta(SST) 3 (OEt) 2 ] (17) where OEt = OCH 2 CH 3 . The group 5 monomeric complexes were solved in a TBPY-5 arrangement, whereas the Ta of the dinculear 16 was solved in an octahedral coordination environment. Thermal analyses of these precursors revealed a stepwise loss of ligand, which indicated their potential utility for generating the MSiO x , materials. The complexes were thermally processed (350 - 1100 °C, 4h, ambient atmosphere) but instead of the desired MSiO x , transmission electron microscopy analyses revealed fractions of the group 4 and group 5 precursors had formed unusual architectures.
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