Highly Condensed Titanoxanes: Synthesis of closo-(Cp*Ti)4O6and Its Transformation to bicyclo -(Cp*Ti)4O5Cl2 with TiCl4as an Oxide Acceptor Reagent

L. M. Babcock; W. G. Klemperer

doi:10.1021/ic00309a047

Highly Condensed Titanoxanes: Synthesis of closo-(CpTi)₄O₆and Its Transformation to bicyclo -(CpTi)₄O₅Cl2 with TiCl₄as an Oxide Acceptor Reagent

L. M. Babcock, W. G. Klemperer

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Abstract

Hydrolysis of Cp*TiCl₃, Cp* = η⁵-C₅(CH₃)₅, under basic conditions yields a titanoxane cage compound, (Cp*Ti)₄0₆(1), having an adamantane-like, tetrahedral Ti₄O₆core structure. This compound reacts with 0.5 equiv of TiCl₄in toluene solution to form the bicyclic species (Cp*Ti)₄O₅Cl (2) in quantitative yield, Here, one oxygen of the Ti₄O₆tetrahedron in 1 has been replaced by two terminal chlorine ligands. Compound 2 reacts with TiCl₄unselectively to produce three new compounds, (Cp*Ti)₄O₄Cl₄(3), (Cp*Ti)₃O₃Cl₃(4), and (Cp*Ti)₂OCl₄(5), plus Cp*TiCl₃. Compound 5 can be isolated from this mixture in analytically pure, crystalline form. Compound 4 can be prepared in high yield from Cp*TiCl₃and excess water in acetone solution.

Original language	English (US)
Pages (from-to)	2003-2007
Number of pages	5
Journal	Inorganic chemistry
Volume	28
Issue number	10
DOIs	https://doi.org/10.1021/ic00309a047
State	Published - May 1 1989
Externally published	Yes

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title = "Highly Condensed Titanoxanes: Synthesis of closo-(Cp*Ti)4O6and Its Transformation to bicyclo -(Cp*Ti)4O5Cl2 with TiCl4as an Oxide Acceptor Reagent",

abstract = "Hydrolysis of Cp*TiCl3, Cp* = η5-C5(CH3)5, under basic conditions yields a titanoxane cage compound, (Cp*Ti)406(1), having an adamantane-like, tetrahedral Ti4O6core structure. This compound reacts with 0.5 equiv of TiCl4in toluene solution to form the bicyclic species (Cp*Ti)4O5Cl (2) in quantitative yield, Here, one oxygen of the Ti4O6tetrahedron in 1 has been replaced by two terminal chlorine ligands. Compound 2 reacts with TiCl4unselectively to produce three new compounds, (Cp*Ti)4O4Cl4(3), (Cp*Ti)3O3Cl3(4), and (Cp*Ti)2OCl4(5), plus Cp*TiCl3. Compound 5 can be isolated from this mixture in analytically pure, crystalline form. Compound 4 can be prepared in high yield from Cp*TiCl3and excess water in acetone solution.",

author = "Babcock, {L. M.} and Klemperer, {W. G.}",

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AU - Babcock, L. M.

AU - Klemperer, W. G.

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N2 - Hydrolysis of Cp*TiCl3, Cp* = η5-C5(CH3)5, under basic conditions yields a titanoxane cage compound, (Cp*Ti)406(1), having an adamantane-like, tetrahedral Ti4O6core structure. This compound reacts with 0.5 equiv of TiCl4in toluene solution to form the bicyclic species (Cp*Ti)4O5Cl (2) in quantitative yield, Here, one oxygen of the Ti4O6tetrahedron in 1 has been replaced by two terminal chlorine ligands. Compound 2 reacts with TiCl4unselectively to produce three new compounds, (Cp*Ti)4O4Cl4(3), (Cp*Ti)3O3Cl3(4), and (Cp*Ti)2OCl4(5), plus Cp*TiCl3. Compound 5 can be isolated from this mixture in analytically pure, crystalline form. Compound 4 can be prepared in high yield from Cp*TiCl3and excess water in acetone solution.

AB - Hydrolysis of Cp*TiCl3, Cp* = η5-C5(CH3)5, under basic conditions yields a titanoxane cage compound, (Cp*Ti)406(1), having an adamantane-like, tetrahedral Ti4O6core structure. This compound reacts with 0.5 equiv of TiCl4in toluene solution to form the bicyclic species (Cp*Ti)4O5Cl (2) in quantitative yield, Here, one oxygen of the Ti4O6tetrahedron in 1 has been replaced by two terminal chlorine ligands. Compound 2 reacts with TiCl4unselectively to produce three new compounds, (Cp*Ti)4O4Cl4(3), (Cp*Ti)3O3Cl3(4), and (Cp*Ti)2OCl4(5), plus Cp*TiCl3. Compound 5 can be isolated from this mixture in analytically pure, crystalline form. Compound 4 can be prepared in high yield from Cp*TiCl3and excess water in acetone solution.

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Highly Condensed Titanoxanes: Synthesis of closo-(CpTi)₄O₆and Its Transformation to bicyclo -(CpTi)₄O₅Cl2 with TiCl₄as an Oxide Acceptor Reagent

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