Dihydrogen and silane addition to base-free, monomeric bis(cyclopentadienyl)titanium oxides

Tamara E. Hanna; Emil Lobkovsky; Paul J. Chirik

doi:10.1021/ic070205+

Dihydrogen and silane addition to base-free, monomeric bis(cyclopentadienyl)titanium oxides

Tamara E. Hanna, Emil Lobkovsky, Paul J. Chirik

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42 Scopus citations

Abstract

Synthesis of a family of monomeric, base-free bis(cyclopentadienyl)titanium oxide complexes, (η⁵-C₅Me₄R) ₂Ti=O (R = ⁱPr, SiMe₃, SiMe₂Ph), has been accomplished by deoxygenation of styrene oxide by the corresponding sandwich compound. One example, (η⁵-C₅Me ₄SiMe₂Ph)₂Ti=O, was characterized by X-ray diffraction. All three complexes undergo clean and facile hydrogenation at 23°C, yielding the titanocene hydroxy hydride complexes (η⁵- C₅Me₄R)₂Ti(OH)H. For (η⁵-C ₅Me₄SiMe₃)₂Ti=O, the kinetics of hydrogenation were first-order in dihydrogen and exhibited a normal, primary kinetic isotope effect of 2.7(3) at 23°C consistent with a 1,2-addition pathway. Isotope effects of the same direction but smaller magnitudes were determined for silane addition.

Original language	English (US)
Pages (from-to)	2359-2361
Number of pages	3
Journal	Inorganic Chemistry
Volume	46
Issue number	7
DOIs	https://doi.org/10.1021/ic070205+
State	Published - Apr 2 2007
Externally published	Yes

All Science Journal Classification (ASJC) codes

Inorganic Chemistry
Physical and Theoretical Chemistry

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@article{b168de62077b471a94fbc6dad5e418f4,

title = "Dihydrogen and silane addition to base-free, monomeric bis(cyclopentadienyl)titanium oxides",

abstract = "Synthesis of a family of monomeric, base-free bis(cyclopentadienyl)titanium oxide complexes, (η5-C5Me4R) 2Ti=O (R = iPr, SiMe3, SiMe2Ph), has been accomplished by deoxygenation of styrene oxide by the corresponding sandwich compound. One example, (η5-C5Me 4SiMe2Ph)2Ti=O, was characterized by X-ray diffraction. All three complexes undergo clean and facile hydrogenation at 23°C, yielding the titanocene hydroxy hydride complexes (η5- C5Me4R)2Ti(OH)H. For (η5-C 5Me4SiMe3)2Ti=O, the kinetics of hydrogenation were first-order in dihydrogen and exhibited a normal, primary kinetic isotope effect of 2.7(3) at 23°C consistent with a 1,2-addition pathway. Isotope effects of the same direction but smaller magnitudes were determined for silane addition.",

author = "Hanna, {Tamara E.} and Emil Lobkovsky and Chirik, {Paul J.}",

year = "2007",

month = apr,

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doi = "10.1021/ic070205+",

language = "English (US)",

volume = "46",

pages = "2359--2361",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "7",

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TY - JOUR

T1 - Dihydrogen and silane addition to base-free, monomeric bis(cyclopentadienyl)titanium oxides

AU - Hanna, Tamara E.

AU - Lobkovsky, Emil

AU - Chirik, Paul J.

PY - 2007/4/2

Y1 - 2007/4/2

N2 - Synthesis of a family of monomeric, base-free bis(cyclopentadienyl)titanium oxide complexes, (η5-C5Me4R) 2Ti=O (R = iPr, SiMe3, SiMe2Ph), has been accomplished by deoxygenation of styrene oxide by the corresponding sandwich compound. One example, (η5-C5Me 4SiMe2Ph)2Ti=O, was characterized by X-ray diffraction. All three complexes undergo clean and facile hydrogenation at 23°C, yielding the titanocene hydroxy hydride complexes (η5- C5Me4R)2Ti(OH)H. For (η5-C 5Me4SiMe3)2Ti=O, the kinetics of hydrogenation were first-order in dihydrogen and exhibited a normal, primary kinetic isotope effect of 2.7(3) at 23°C consistent with a 1,2-addition pathway. Isotope effects of the same direction but smaller magnitudes were determined for silane addition.

AB - Synthesis of a family of monomeric, base-free bis(cyclopentadienyl)titanium oxide complexes, (η5-C5Me4R) 2Ti=O (R = iPr, SiMe3, SiMe2Ph), has been accomplished by deoxygenation of styrene oxide by the corresponding sandwich compound. One example, (η5-C5Me 4SiMe2Ph)2Ti=O, was characterized by X-ray diffraction. All three complexes undergo clean and facile hydrogenation at 23°C, yielding the titanocene hydroxy hydride complexes (η5- C5Me4R)2Ti(OH)H. For (η5-C 5Me4SiMe3)2Ti=O, the kinetics of hydrogenation were first-order in dihydrogen and exhibited a normal, primary kinetic isotope effect of 2.7(3) at 23°C consistent with a 1,2-addition pathway. Isotope effects of the same direction but smaller magnitudes were determined for silane addition.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 7

ER -

Dihydrogen and silane addition to base-free, monomeric bis(cyclopentadienyl)titanium oxides

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