Titanium(IV) Neopentoxides. X-ray Structures of Ti₃(μ₃-O)(μ₃-Cl)(μ-OCH₂CMe₃)₃(OCH₂CMe₃)₆and [Ti(μ-OCH₂CMe₃)(OCH₂CMe₃)₃]₂

Abstract

Attempts to synthesize titanium(IV) neopentoxide led to two unique products which were crystallographically characterized. A metathesis reaction between TiCl(4) and NaOCH(2)CMe(3) (NaONp) yielded Ti(3)(O)(Cl)(ONp)(9).C(7)H(8), 1, which adopts a standard M(3)(&mgr;(3)-X)(2)(&mgr;-X)(3)X(6) structure. The &mgr;(3) ligands are a Cl and an O atom, with the rest of ligands represented by bridging and terminal ONp ligands. [Ti(ONp)(4)](2), 2, was isolated in high yield by an alcoholysis exchange between Ti(OPr(i))(4) and HONp. 2 adopts a typical M(2)(&mgr;-X)(2)(X)(6) fused axial-equatorial edge-shared geometry, wherein each metal center is 5 coordinated. On the basis of molecular weight solution studies and (1)H, (13)C, (17)O (natural abundance), and (47,49)Ti solution and solid-state NMR investigations, 2 was determined to be a monomer in solution.

Neo-pentoxide Precursors for MOCVD Thin Films of TiO2 and ZrO2

“…Compound 1 is a solid at room temperature and was found to possess high volatility at low temperatures and was reportedly more air stable than TTIP. [20] This stability has been attributed to the steric bulk of the ONep ligand. Structural and solution studies of primary alkoxide ONep versus secondary alkoxide O i Pr-ligated compounds reveal that ONep species adopt smaller oligomers and demonstrate reduced reactivity with ambient moisture.…”

“…Structural and solution studies of primary alkoxide ONep versus secondary alkoxide O i Pr-ligated compounds reveal that ONep species adopt smaller oligomers and demonstrate reduced reactivity with ambient moisture. [18,20] These phenomena have been explained by considering two aspects of the ONep ligand. [18,20] First the tert-butyl groups of the ONep ligand in the b-position are free to rotate and will sweep out an area around the metal center that is greater than that of the two methyls in the a-position of the O Pr analogs.…”

“…In particular, we have isolated several new powder precursors that demonstrate improved volatility through the introduction of the neo-pentoxide (OCH 2 CMe 3 = ONep) ligand. Two group IV ONep derivatives that were found to possess low melting points and low vaporization temperatures are [Ti(m-ONep)(ONep) 3 ] 2 (1) [20] and (2). [21] Figure 1 is a schematic representation of the structures of 1 and 2.…”

Formation and Structural Characterisation of an Unusual Cyclic HexamericOxotitanium Complex

“…This compound was obtained by the hydrolysis alkoxide fragments. The modification involves the introduc-and condensation of Ti(MDEA) 2 (2) prepared from the retion of bi-or multidentate anionic ligands, such that the action of Ti(OPr) 4 with two equivalents of MDEAH 2 . It is reactivity of the resulting compound is lower than the par-difficult to be definitive about the sequence of substitution ent alkoxide thus allowing size control of the primarily and hydrolysis reactions occurring, but it seems necessary formed oxo-particles.…”

“…It is reactivity of the resulting compound is lower than the par-difficult to be definitive about the sequence of substitution ent alkoxide thus allowing size control of the primarily and hydrolysis reactions occurring, but it seems necessary formed oxo-particles. Examples of titanium oxo-complexes to first form the bis MDEA complex from Ti(OPr) 4 , which include oxo-alkoxides, [1Ϫ5] β-diketonates,…”