Syntheses, crystal structure and theoretical modelling of tetrahedral mono-β-diketonato titanocenyl complexes

Annemarie Kuhn; Alfred Muller; Jeanet Conradie

doi:10.1016/j.poly.2008.12.060

Syntheses, crystal structure and theoretical modelling of tetrahedral mono-β-diketonato titanocenyl complexes

Annemarie Kuhn, Alfred Muller, Jeanet Conradie

University of The Free State

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

9 Citations (Scopus)

Abstract

A comparative investigation on three novel bis(cyclopentadienyl) mono(β-diketonato) titanium(IV) complexes, [Cp₂Ti^IV(R¹COCHCOR²)] ⁺ClO₄^- (Cp = η⁵-C₅H₅), i.e. [Cp₂Ti(tfba)]⁺, [Cp₂Ti(tfth)]⁺ and [Cp₂Ti(tfba)]⁺ where tfba = CF₃COCHCOC₆H₅^-, tfth = CF₃COCHCOC₄H₃S^- and tffu = CF₃COCHCOC₄H₃O^-, has been performed based on structural data and DFT calculations. The preparation of [Cp₂Ti^IV(β-diketonato)]⁺ClO ₄^- involves the reaction of Cp₂TiCl₂ with AgClO₄ and the respective β-diketones. The crystal structures show that the structures are isomorphous. All the complexes exhibit π-stacking between one Cp ring and the aromatic R-group ring, i.e. the C₆H₅, C₄H₃S and C₄H₃O fragments, respectively. The DFT calculations show that the formal 16-electron count of these d⁰ titanium(IV) complexes is increased via Ti ← O π bonding. The bonding mode in the [Cp₂Ti(β-diketonato)]⁺ complexes is different from that in Cp₂Ti(OR)₂ and Cp₂Ti(dioxolene) complexes.

Original language	English
Pages (from-to)	966-974
Number of pages	9
Journal	Polyhedron
Volume	28
Issue number	5
DOIs	https://doi.org/10.1016/j.poly.2008.12.060
Publication status	Published - 1 Apr 2009
Externally published	Yes

Keywords

Crystal structure
DFT
Titanocene
β-Diketone

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.poly.2008.12.060

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title = "Syntheses, crystal structure and theoretical modelling of tetrahedral mono-β-diketonato titanocenyl complexes",

abstract = "A comparative investigation on three novel bis(cyclopentadienyl) mono(β-diketonato) titanium(IV) complexes, [Cp2TiIV(R1COCHCOR2)] +ClO4- (Cp = η5-C5H5), i.e. [Cp2Ti(tfba)]+, [Cp2Ti(tfth)]+ and [Cp2Ti(tfba)]+ where tfba = CF3COCHCOC6H5-, tfth = CF3COCHCOC4H3S- and tffu = CF3COCHCOC4H3O-, has been performed based on structural data and DFT calculations. The preparation of [Cp2TiIV(β-diketonato)]+ClO 4- involves the reaction of Cp2TiCl2 with AgClO4 and the respective β-diketones. The crystal structures show that the structures are isomorphous. All the complexes exhibit π-stacking between one Cp ring and the aromatic R-group ring, i.e. the C6H5, C4H3S and C4H3O fragments, respectively. The DFT calculations show that the formal 16-electron count of these d0 titanium(IV) complexes is increased via Ti ← O π bonding. The bonding mode in the [Cp2Ti(β-diketonato)]+ complexes is different from that in Cp2Ti(OR)2 and Cp2Ti(dioxolene) complexes.",

keywords = "Crystal structure, DFT, Titanocene, β-Diketone",

author = "Annemarie Kuhn and Alfred Muller and Jeanet Conradie",

year = "2009",

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T1 - Syntheses, crystal structure and theoretical modelling of tetrahedral mono-β-diketonato titanocenyl complexes

AU - Kuhn, Annemarie

AU - Muller, Alfred

AU - Conradie, Jeanet

PY - 2009/4/1

Y1 - 2009/4/1

N2 - A comparative investigation on three novel bis(cyclopentadienyl) mono(β-diketonato) titanium(IV) complexes, [Cp2TiIV(R1COCHCOR2)] +ClO4- (Cp = η5-C5H5), i.e. [Cp2Ti(tfba)]+, [Cp2Ti(tfth)]+ and [Cp2Ti(tfba)]+ where tfba = CF3COCHCOC6H5-, tfth = CF3COCHCOC4H3S- and tffu = CF3COCHCOC4H3O-, has been performed based on structural data and DFT calculations. The preparation of [Cp2TiIV(β-diketonato)]+ClO 4- involves the reaction of Cp2TiCl2 with AgClO4 and the respective β-diketones. The crystal structures show that the structures are isomorphous. All the complexes exhibit π-stacking between one Cp ring and the aromatic R-group ring, i.e. the C6H5, C4H3S and C4H3O fragments, respectively. The DFT calculations show that the formal 16-electron count of these d0 titanium(IV) complexes is increased via Ti ← O π bonding. The bonding mode in the [Cp2Ti(β-diketonato)]+ complexes is different from that in Cp2Ti(OR)2 and Cp2Ti(dioxolene) complexes.

AB - A comparative investigation on three novel bis(cyclopentadienyl) mono(β-diketonato) titanium(IV) complexes, [Cp2TiIV(R1COCHCOR2)] +ClO4- (Cp = η5-C5H5), i.e. [Cp2Ti(tfba)]+, [Cp2Ti(tfth)]+ and [Cp2Ti(tfba)]+ where tfba = CF3COCHCOC6H5-, tfth = CF3COCHCOC4H3S- and tffu = CF3COCHCOC4H3O-, has been performed based on structural data and DFT calculations. The preparation of [Cp2TiIV(β-diketonato)]+ClO 4- involves the reaction of Cp2TiCl2 with AgClO4 and the respective β-diketones. The crystal structures show that the structures are isomorphous. All the complexes exhibit π-stacking between one Cp ring and the aromatic R-group ring, i.e. the C6H5, C4H3S and C4H3O fragments, respectively. The DFT calculations show that the formal 16-electron count of these d0 titanium(IV) complexes is increased via Ti ← O π bonding. The bonding mode in the [Cp2Ti(β-diketonato)]+ complexes is different from that in Cp2Ti(OR)2 and Cp2Ti(dioxolene) complexes.

KW - Crystal structure

KW - DFT

KW - Titanocene

KW - β-Diketone

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DO - 10.1016/j.poly.2008.12.060

M3 - Article

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SN - 0277-5387

VL - 28

SP - 966

EP - 974

JO - Polyhedron

JF - Polyhedron

IS - 5

ER -

Syntheses, crystal structure and theoretical modelling of tetrahedral mono-β-diketonato titanocenyl complexes

Abstract

Keywords

ASJC Scopus subject areas

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