Group 4 Metal and Lanthanide Complexes in the Oxidation State +3 with Tris(trimethylsilyl)silyl Ligands

Rainer Zitz, Johann Hlina, Henning Arp, Dominik Kinschel, Christoph Marschner, Judith Baumgartner

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Abstract

A number of paramagnetic silylated d 1 group 4 metallates were prepared by reaction of potassium tris(trimethylsilyl)silanide with group 4 metallates of the type K[Cp 2 MCl 2 ] (M = Ti, Zr, Hf). The outcomes of the reactions differ for all three metals. While for the hafnium case the expected complex [Cp 2 Hf{Si(SiMe 3 ) 3 } 2 ] - was obtained, the analogous titanium reaction led to a product with two Si(H)(SiMe 3 ) 2 ligands. The reaction with zirconium caused the formation of a dinuclear fulvalene bridged complex. The desired [Cp 2 Zr{Si(SiMe 3 ) 3 } 2 ] - could be obtained by reduction of Cp 2 Zr{Si(SiMe 3 ) 3 } 2 with potassium. In related reactions of potassium tris(trimethylsilyl)silanide with some lanthanidocenes Cp 3 Ln (Ln = Ce, Sm, Gd, Ho, Tm) complexes of the type [Cp 3 Ln Si(SiMe 3 ) 3 ] - with either [18-crown-6·K] + or the complex ion [18-crown-6·K·Cp·K·18-crown-6] as counterions were obtained. Due to d 1 or f n electron configuration, unambiguous characterization of all obtained complexes could only be achieved by single crystal XRD diffraction analysis.

Original languageEnglish
Pages (from-to)7107-7117
Number of pages11
JournalInorganic chemistry
Volume58
Issue number10
DOIs
Publication statusPublished - May 2019

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Lanthanoid Series Elements
Potassium
Metals
Ligands
Oxidation
ligands
oxidation
Hafnium
potassium
metals
Titanium
Diffraction
Single crystals
Ions
hafnium
Electrons
titanium
single crystals
products
configurations

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Group 4 Metal and Lanthanide Complexes in the Oxidation State +3 with Tris(trimethylsilyl)silyl Ligands. / Zitz, Rainer; Hlina, Johann; Arp, Henning; Kinschel, Dominik; Marschner, Christoph; Baumgartner, Judith.

In: Inorganic chemistry, Vol. 58, No. 10, 05.2019, p. 7107-7117.

Research output: Contribution to journalArticleResearchpeer-review

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abstract = "A number of paramagnetic silylated d 1 group 4 metallates were prepared by reaction of potassium tris(trimethylsilyl)silanide with group 4 metallates of the type K[Cp 2 MCl 2 ] (M = Ti, Zr, Hf). The outcomes of the reactions differ for all three metals. While for the hafnium case the expected complex [Cp 2 Hf{Si(SiMe 3 ) 3 } 2 ] - was obtained, the analogous titanium reaction led to a product with two Si(H)(SiMe 3 ) 2 ligands. The reaction with zirconium caused the formation of a dinuclear fulvalene bridged complex. The desired [Cp 2 Zr{Si(SiMe 3 ) 3 } 2 ] - could be obtained by reduction of Cp 2 Zr{Si(SiMe 3 ) 3 } 2 with potassium. In related reactions of potassium tris(trimethylsilyl)silanide with some lanthanidocenes Cp 3 Ln (Ln = Ce, Sm, Gd, Ho, Tm) complexes of the type [Cp 3 Ln Si(SiMe 3 ) 3 ] - with either [18-crown-6·K] + or the complex ion [18-crown-6·K·Cp·K·18-crown-6] as counterions were obtained. Due to d 1 or f n electron configuration, unambiguous characterization of all obtained complexes could only be achieved by single crystal XRD diffraction analysis.",
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AU - Marschner, Christoph

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AB - A number of paramagnetic silylated d 1 group 4 metallates were prepared by reaction of potassium tris(trimethylsilyl)silanide with group 4 metallates of the type K[Cp 2 MCl 2 ] (M = Ti, Zr, Hf). The outcomes of the reactions differ for all three metals. While for the hafnium case the expected complex [Cp 2 Hf{Si(SiMe 3 ) 3 } 2 ] - was obtained, the analogous titanium reaction led to a product with two Si(H)(SiMe 3 ) 2 ligands. The reaction with zirconium caused the formation of a dinuclear fulvalene bridged complex. The desired [Cp 2 Zr{Si(SiMe 3 ) 3 } 2 ] - could be obtained by reduction of Cp 2 Zr{Si(SiMe 3 ) 3 } 2 with potassium. In related reactions of potassium tris(trimethylsilyl)silanide with some lanthanidocenes Cp 3 Ln (Ln = Ce, Sm, Gd, Ho, Tm) complexes of the type [Cp 3 Ln Si(SiMe 3 ) 3 ] - with either [18-crown-6·K] + or the complex ion [18-crown-6·K·Cp·K·18-crown-6] as counterions were obtained. Due to d 1 or f n electron configuration, unambiguous characterization of all obtained complexes could only be achieved by single crystal XRD diffraction analysis.

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