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Controlled synthesis of a structurally characterized family of sterically constrained heterocyclic alkoxy-modified titanium alkoxides.
Boyle, Timothy J; Sewell, Robin M; Ottley, Leigh Anna M; Pratt, Harry D; Quintana, Christopher J; Bunge, Scott D.
Afiliación
  • Boyle TJ; Sandia National Laboratories, Advanced Materials Laboratory, 1001 University Boulevard SE, Albuquerque, New Mexico 87106, USA. tjboyle@Sandia.gov
Inorg Chem ; 46(5): 1825-35, 2007 Mar 05.
Article en En | MEDLINE | ID: mdl-17319735
The reaction of [Ti(mu-ONep)(ONep)3]2 (ONep = OCH2C(CH3)3) with a series of heterocyclic methanol derivatives [tetrahydrofurfuryl alcohol (H-OTHF), thiophene methanol (H-OTPM), or 2-pyridylcarbinol (H-OPy)-collectively termed H-OR*], led to the isolation of a novel family of OR*-substituted titanium alkoxide precursors. Independent of the initial stoichiometry for the H-OTHF reaction, a monosubstituted, dinuclear species was isolated as [(ONep)3Ti(muc-OTHF)]2 (1). For 1, each Ti was octahedrally (Oh) bound by three terminal ONep ligands, one bidentate bridging OTHF ligand (muc-OTHF), and an oxygen from the other muc-OTHF ligand. For the OTPM derivatives, the product was identified as [(ONep)3Ti(mu-OTPM)]2 (2). For this ligand, the soft S atom does not bind to the Ti but the O atom does act as a bridge between the two trigonal bipyramidal bound Ti metal centers. The OPy system yielded (OPy)2Ti(OR)2 independent of the OR and the stoichiometry used [OR = ONep (3), OCHMe2 (4), OCMe3 (5)]. For 3-5, the two OPy ligands chelate to the Oh-bound Ti metal center with two terminal OR ligands. Compounds 1-5 were fully characterized using a variety of analytical techniques. An initial investigation of the proposed chemical stability of the '(OPy)2Ti' moiety of 3-5 to alcoholysis exchange pathways involving (i) alkyl alcohols, (ii) aryl alcohols, (iii) substituted phenols, (iv) H-OR* derivatives, and (v) silanols proved successful through the isolation of a novel family of structurally characterized (OPy)2Ti(OR')2 (7-24) compounds.
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Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Compuestos Organometálicos / Óxidos / Titanio / Compuestos Heterocíclicos Idioma: En Revista: Inorg Chem Año: 2007 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos
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Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Compuestos Organometálicos / Óxidos / Titanio / Compuestos Heterocíclicos Idioma: En Revista: Inorg Chem Año: 2007 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos