Synthesis, crystal structure and electrochemistry of tetrahedral mono-β-diketonato titanocenyl complexes

Elizabeth Erasmus; Jeanet Conradie; Alfred Muller; Jannie C. Swarts

doi:10.1016/j.ica.2006.11.010

Synthesis, crystal structure and electrochemistry of tetrahedral mono-β-diketonato titanocenyl complexes

Elizabeth Erasmus, Jeanet Conradie, Alfred Muller, Jannie C. Swarts

University of The Free State

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

35 Citations (Scopus)

Abstract

The synthesis of a variety of tetrahedral β-diketonato titanium(IV) complexes of the type [(C₅ H₅)₂ Ti (CH₃ COCHCOR)]⁺ ClO₄^- with R = CF₃, OCH₃, C₆H₅, CH₃ and Fc is described. The Ti^III/Ti^IV couples and the Fc/Fc⁺ couple exhibited chemically and electrochemically reversible cyclic voltammetric behaviour. The formal reduction potential of the Ti^III/IV couple increased as the group electronegativity of the R group of the β-diketonato ligand increased. Bulk electrolysis showed that one electron was transferred in the Ti^III/IV couple and one electron in the ferrocenyl/ferrocenium redox couple in the ligand. The crystal structure for the R = OCH₃ complex showed that this β-keto-ester binds through the carbonyl oxygen of the ester group and not the ether oxygen.

Original language	English
Pages (from-to)	2277-2283
Number of pages	7
Journal	Inorganica Chimica Acta
Volume	360
Issue number	7
DOIs	https://doi.org/10.1016/j.ica.2006.11.010
Publication status	Published - 2 May 2007
Externally published	Yes

Keywords

Crystal structure
Cyclic voltammetry
Titanocene
β-diketonates

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.ica.2006.11.010

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title = "Synthesis, crystal structure and electrochemistry of tetrahedral mono-β-diketonato titanocenyl complexes",

abstract = "The synthesis of a variety of tetrahedral β-diketonato titanium(IV) complexes of the type [(C5 H5)2 Ti (CH3 COCHCOR)]+ ClO4- with R = CF3, OCH3, C6H5, CH3 and Fc is described. The TiIII/TiIV couples and the Fc/Fc+ couple exhibited chemically and electrochemically reversible cyclic voltammetric behaviour. The formal reduction potential of the TiIII/IV couple increased as the group electronegativity of the R group of the β-diketonato ligand increased. Bulk electrolysis showed that one electron was transferred in the TiIII/IV couple and one electron in the ferrocenyl/ferrocenium redox couple in the ligand. The crystal structure for the R = OCH3 complex showed that this β-keto-ester binds through the carbonyl oxygen of the ester group and not the ether oxygen.",

keywords = "Crystal structure, Cyclic voltammetry, Titanocene, β-diketonates",

author = "Elizabeth Erasmus and Jeanet Conradie and Alfred Muller and Swarts, {Jannie C.}",

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T1 - Synthesis, crystal structure and electrochemistry of tetrahedral mono-β-diketonato titanocenyl complexes

AU - Erasmus, Elizabeth

AU - Conradie, Jeanet

AU - Muller, Alfred

AU - Swarts, Jannie C.

PY - 2007/5/2

Y1 - 2007/5/2

N2 - The synthesis of a variety of tetrahedral β-diketonato titanium(IV) complexes of the type [(C5 H5)2 Ti (CH3 COCHCOR)]+ ClO4- with R = CF3, OCH3, C6H5, CH3 and Fc is described. The TiIII/TiIV couples and the Fc/Fc+ couple exhibited chemically and electrochemically reversible cyclic voltammetric behaviour. The formal reduction potential of the TiIII/IV couple increased as the group electronegativity of the R group of the β-diketonato ligand increased. Bulk electrolysis showed that one electron was transferred in the TiIII/IV couple and one electron in the ferrocenyl/ferrocenium redox couple in the ligand. The crystal structure for the R = OCH3 complex showed that this β-keto-ester binds through the carbonyl oxygen of the ester group and not the ether oxygen.

AB - The synthesis of a variety of tetrahedral β-diketonato titanium(IV) complexes of the type [(C5 H5)2 Ti (CH3 COCHCOR)]+ ClO4- with R = CF3, OCH3, C6H5, CH3 and Fc is described. The TiIII/TiIV couples and the Fc/Fc+ couple exhibited chemically and electrochemically reversible cyclic voltammetric behaviour. The formal reduction potential of the TiIII/IV couple increased as the group electronegativity of the R group of the β-diketonato ligand increased. Bulk electrolysis showed that one electron was transferred in the TiIII/IV couple and one electron in the ferrocenyl/ferrocenium redox couple in the ligand. The crystal structure for the R = OCH3 complex showed that this β-keto-ester binds through the carbonyl oxygen of the ester group and not the ether oxygen.

KW - Crystal structure

KW - Cyclic voltammetry

KW - Titanocene

KW - β-diketonates

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U2 - 10.1016/j.ica.2006.11.010

DO - 10.1016/j.ica.2006.11.010

M3 - Article

AN - SCOPUS:34147161299

SN - 0020-1693

VL - 360

SP - 2277

EP - 2283

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

IS - 7

ER -

Synthesis, crystal structure and electrochemistry of tetrahedral mono-β-diketonato titanocenyl complexes

Abstract

Keywords

ASJC Scopus subject areas

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