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

Research output: Contribution to journal › Article › peer-review

48 Scopus citations

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to form the bicyclic species (Cp*Ti)₄O₅Cl (2) in quantitative yield, Here, one oxygen of the Ti₄O₆tetrahedron in 1 has been replaced by two terminal chlorine ligands.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

Publisher link

10.1021/ic00309a047

Find It

Find It at U of M Libraries

Cite this

@article{52857bfa68c44b68b6c1388f6cd06c48,

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to form the bicyclic species (Cp*Ti)4O5Cl (2) in quantitative yield, Here, one oxygen of the Ti4O6tetrahedron in 1 has been replaced by two terminal chlorine ligands.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.\}",

year = "1989",

month = may,

day = "1",

doi = "10.1021/ic00309a047",

language = "English (US)",

volume = "28",

pages = "2003--2007",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "10",

}

TY - JOUR

T1 - Highly Condensed Titanoxanes

T2 - Synthesis of closo-(Cp*Ti)4O6and Its Transformation to bicyclo -(Cp*Ti)4O5Cl2 with TiCl4as an Oxide Acceptor Reagent

AU - Babcock, L. M.

AU - Klemperer, W. G.

PY - 1989/5/1

Y1 - 1989/5/1

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.

UR - https://www.scopus.com/pages/publications/33845183947

UR - https://www.scopus.com/pages/publications/33845183947#tab=citedBy

U2 - 10.1021/ic00309a047

DO - 10.1021/ic00309a047

M3 - Article

AN - SCOPUS:33845183947

SN - 0020-1669

VL - 28

SP - 2003

EP - 2007

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 10

ER -

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

Abstract

Publisher link

Find It

Other files and links

Fingerprint

Cite this