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 journalArticle

9 Citations (Scopus)

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 languageEnglish (US)
Pages (from-to)1356-1365
Number of pages10
JournalPolyhedron
Volume24
Issue number11
DOIs
StatePublished - Aug 4 2005
Externally publishedYes

Fingerprint

Titanium compounds
titanium compounds
Ligands
ligands
Deuterium
rings
Bond length
synthesis
Titanium
Hydrides
X-Ray Diffraction
hydrides
deuterium
elimination
Hot Temperature
methylidyne
X ray diffraction
Hydrogen
Temperature
room temperature

Keywords

  • Ansa
  • Fulrene
  • Metallocene
  • Pyrrolyl
  • Titanium
  • Titanocene

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

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.; Churchill, David G.; Parkin, Gerard.

In: Polyhedron, Vol. 24, No. 11, 04.08.2005, p. 1356-1365.

Research output: Contribution to journalArticle

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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",
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TY - JOUR

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

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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SP - 1356

EP - 1365

JO - Polyhedron

JF - Polyhedron

SN - 0277-5387

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