Titanium(IV) Neopentoxides. X-ray Structures of Ti33-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 TiCl4 and NaOCH2CMe3 (NaONp) yielded Ti3(O)(Cl)(ONp)9·C7H8, 1, which adopts a standard M33-X)2(μ-X)3X6 structure. The μ3 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(OPri)4 and HONp. 2 adopts a typical M2(μ-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 1H, 13C, 17O (natural abundance), and 47,49Ti solution and solid-state NMR investigations, 2 was determined to be a monomer in solution.

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