Ansa-titanocene pyrrolyl complexes: The synthesis and structural characterization of [Me2Si(C5Me4) 2]Ti(NC4H4)X (X = H, Me, Cl and NC 4H4) and [Me2Si(C5Me 4)(C5Me3CH2)]Ti(NC4H 4)

Hyosun Lee; Jeffrey B. Bonanno; Brian M. Bridgewater; David G. Churchill; Gerard Parkin

doi:10.1016/j.poly.2005.04.005

Ansa-titanocene pyrrolyl complexes: The synthesis and structural characterization of [Me₂Si(C₅Me₄) ₂]Ti(NC₄H₄)X (X = H, Me, Cl and NC ₄H₄) and [Me₂Si(C₅Me ₄)(C₅Me₃CH₂)]Ti(NC₄H ₄)

Hyosun Lee, Jeffrey B. Bonanno, Brian M. Bridgewater, David G. Churchill, Gerard Parkin

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

11 Scopus citations

Abstract

A series of titanium-pyrrolyl compounds, namely [Me₂Si(C ₅Me₄)₂]Ti(NC₄H₄)X (X = H, Me, Cl, NC₄H₄) and [Me₂Si(C₅Me ₄)(C₅Me₃CH₂)]Ti(NC₄H ₄) has been synthesized and structurally characterized by X-ray diffraction. Analysis of the TiNC₄H₄ bond lengths in these complexes indicates that pyrrolyl does not, by comparison to dialkylamido, act as an efficient π-donor ligand. The fulvene complex [Me₂Si(C ₅Me₄)(C₅Me₃CH₂)] Ti(NC₄H₄) is obtained via thermal elimination of CH ₄ and H₂ from [Me₂Si(C₅Me ₄)₂]Ti(NC₄H₄)Me and [Me ₂Si(C₅Me₄)₂]Ti(NC₄H ₄)H, respectively. The latter transformation is reversible, with [Me₂Si(C₅Me₄)(C₅Me ₃CH₂)]Ti(NC₄H₄) reacting with H ₂ to give [Me₂Si(C₅Me₄) ₂]Ti(NC₄H₄)H at room temperature. In accord with this reversibility, treatment of [Me₂Si(C₅Me ₄)₂]Ti(NC₄H₄)H with D₂ results in incorporation of deuterium into the hydride and one ring methyl group of each cyclopentadienyl ring of the [Me₂Si(C₅Me ₄)₂] ligand.

Original language	English (US)
Pages (from-to)	1356-1365
Number of pages	10
Journal	Polyhedron
Volume	24
Issue number	11
DOIs	https://doi.org/10.1016/j.poly.2005.04.005
State	Published - Aug 4 2005
Externally published	Yes

Keywords

Ansa
Fulrene
Metallocene
Pyrrolyl
Titanium
Titanocene

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/j.poly.2005.04.005

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Ansa-titanocene pyrrolyl complexes: The synthesis and structural characterization of [Me₂Si(C₅Me₄) ₂]Ti(NC₄H₄)X (X = H, Me, Cl and NC ₄H₄) and [Me₂Si(C₅Me ₄)(C₅Me₃CH₂)]Ti(NC₄H ₄). / Lee, Hyosun; Bonanno, Jeffrey B.; Bridgewater, Brian M. et al.
In: Polyhedron, Vol. 24, No. 11, 04.08.2005, p. 1356-1365.

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

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title = "Ansa-titanocene pyrrolyl complexes: The synthesis and structural characterization of [Me2Si(C5Me4) 2]Ti(NC4H4)X (X = H, Me, Cl and NC 4H4) and [Me2Si(C5Me 4)(C5Me3CH2)]Ti(NC4H 4)",

abstract = "A series of titanium-pyrrolyl compounds, namely [Me2Si(C 5Me4)2]Ti(NC4H4)X (X = H, Me, Cl, NC4H4) and [Me2Si(C5Me 4)(C5Me3CH2)]Ti(NC4H 4) has been synthesized and structurally characterized by X-ray diffraction. Analysis of the TiNC4H4 bond lengths in these complexes indicates that pyrrolyl does not, by comparison to dialkylamido, act as an efficient π-donor ligand. The fulvene complex [Me2Si(C 5Me4)(C5Me3CH2)] Ti(NC4H4) is obtained via thermal elimination of CH 4 and H2 from [Me2Si(C5Me 4)2]Ti(NC4H4)Me and [Me 2Si(C5Me4)2]Ti(NC4H 4)H, respectively. The latter transformation is reversible, with [Me2Si(C5Me4)(C5Me 3CH2)]Ti(NC4H4) reacting with H 2 to give [Me2Si(C5Me4) 2]Ti(NC4H4)H at room temperature. In accord with this reversibility, treatment of [Me2Si(C5Me 4)2]Ti(NC4H4)H with D2 results in incorporation of deuterium into the hydride and one ring methyl group of each cyclopentadienyl ring of the [Me2Si(C5Me 4)2] ligand.",

keywords = "Ansa, Fulrene, Metallocene, Pyrrolyl, Titanium, Titanocene",

author = "Hyosun Lee and Bonanno, {Jeffrey B.} and Bridgewater, {Brian M.} and Churchill, {David G.} and Gerard Parkin",

note = "Funding Information: We thank the US Department of Energy, Office of Basic Energy Sciences (DE-FG02-93ER14339) for support of this research.",

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T1 - Ansa-titanocene pyrrolyl complexes

T2 - The synthesis and structural characterization of [Me2Si(C5Me4) 2]Ti(NC4H4)X (X = H, Me, Cl and NC 4H4) and [Me2Si(C5Me 4)(C5Me3CH2)]Ti(NC4H 4)

AU - Lee, Hyosun

AU - Bonanno, Jeffrey B.

AU - Bridgewater, Brian M.

AU - Churchill, David G.

AU - Parkin, Gerard

N1 - Funding Information: We thank the US Department of Energy, Office of Basic Energy Sciences (DE-FG02-93ER14339) for support of this research.

PY - 2005/8/4

Y1 - 2005/8/4

N2 - A series of titanium-pyrrolyl compounds, namely [Me2Si(C 5Me4)2]Ti(NC4H4)X (X = H, Me, Cl, NC4H4) and [Me2Si(C5Me 4)(C5Me3CH2)]Ti(NC4H 4) has been synthesized and structurally characterized by X-ray diffraction. Analysis of the TiNC4H4 bond lengths in these complexes indicates that pyrrolyl does not, by comparison to dialkylamido, act as an efficient π-donor ligand. The fulvene complex [Me2Si(C 5Me4)(C5Me3CH2)] Ti(NC4H4) is obtained via thermal elimination of CH 4 and H2 from [Me2Si(C5Me 4)2]Ti(NC4H4)Me and [Me 2Si(C5Me4)2]Ti(NC4H 4)H, respectively. The latter transformation is reversible, with [Me2Si(C5Me4)(C5Me 3CH2)]Ti(NC4H4) reacting with H 2 to give [Me2Si(C5Me4) 2]Ti(NC4H4)H at room temperature. In accord with this reversibility, treatment of [Me2Si(C5Me 4)2]Ti(NC4H4)H with D2 results in incorporation of deuterium into the hydride and one ring methyl group of each cyclopentadienyl ring of the [Me2Si(C5Me 4)2] ligand.

AB - A series of titanium-pyrrolyl compounds, namely [Me2Si(C 5Me4)2]Ti(NC4H4)X (X = H, Me, Cl, NC4H4) and [Me2Si(C5Me 4)(C5Me3CH2)]Ti(NC4H 4) has been synthesized and structurally characterized by X-ray diffraction. Analysis of the TiNC4H4 bond lengths in these complexes indicates that pyrrolyl does not, by comparison to dialkylamido, act as an efficient π-donor ligand. The fulvene complex [Me2Si(C 5Me4)(C5Me3CH2)] Ti(NC4H4) is obtained via thermal elimination of CH 4 and H2 from [Me2Si(C5Me 4)2]Ti(NC4H4)Me and [Me 2Si(C5Me4)2]Ti(NC4H 4)H, respectively. The latter transformation is reversible, with [Me2Si(C5Me4)(C5Me 3CH2)]Ti(NC4H4) reacting with H 2 to give [Me2Si(C5Me4) 2]Ti(NC4H4)H at room temperature. In accord with this reversibility, treatment of [Me2Si(C5Me 4)2]Ti(NC4H4)H with D2 results in incorporation of deuterium into the hydride and one ring methyl group of each cyclopentadienyl ring of the [Me2Si(C5Me 4)2] ligand.

KW - Ansa

KW - Fulrene

KW - Metallocene

KW - Pyrrolyl

KW - Titanium

KW - Titanocene

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