Synthese und struktur von dicyclopentadienyl(trimethylsilyl)titanchlorid

Rösch, L.; Altnau, Gerald; Erb, Wolfgang; Pickardt, Joachim; Bruncks, Norbert

doi:10.1016/s0022-328x(00)84454-x

Cited by 41 publications

(32 citation statements)

References 21 publications

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“…51 The distances of 2.664(2) and 2.674(3) Å, found for 3a , are close to that found for Cp 2 Ti(Cl)SiMe 3 (2.67(1) Å). 6…”

Section: Resultsmentioning

confidence: 99%

“…Investigations on the chemistry of group 4 silyl complexes were started in the late 1960s, with some work on silyl titanium chemistry 1−6 and Lappert’s contributions of zirconocene and hafnocene complexes. 7−10 Systematic studies of zirconocene and hafnocene silyl complexes were carried out by Tilley and co-workers, 11−17 who especially studied aspects of σ-bond metathesis and the catalytic dehydrocoupling polymerization of hydrosilanes catalyzed by these compounds.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2019

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A number of paramagnetic silylated d1 group 4 metallates were prepared by reaction of potassium tris(trimethylsilyl)silanide with group 4 metallates of the type K[Cp2MCl2] (M = Ti, Zr, Hf). The outcomes of the reactions differ for all three metals. While for the hafnium case the expected complex [Cp2Hf{Si(SiMe3)3}2]− was obtained, the analogous titanium reaction led to a product with two Si(H)(SiMe3)2 ligands. The reaction with zirconium caused the formation of a dinuclear fulvalene bridged complex. The desired [Cp2Zr{Si(SiMe3)3}2]− could be obtained by reduction of Cp2Zr{Si(SiMe3)3}2 with potassium. In related reactions of potassium tris(trimethylsilyl)silanide with some lanthanidocenes Cp3Ln (Ln = Ce, Sm, Gd, Ho, Tm) complexes of the type [Cp3Ln Si(SiMe3)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 d1 or fn electron configuration, unambiguous characterization of all obtained complexes could only be achieved by single crystal XRD diffraction analysis.

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“…51 The distances of 2.664(2) and 2.674(3) Å, found for 3a , are close to that found for Cp 2 Ti(Cl)SiMe 3 (2.67(1) Å). 6…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

et al. 2019

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“…Therefore, it is not surprising that the protagonists in these fields are also largely the same. Cp 2 Ti(Cl)SiMe 3 was obtained by Rösch and co-workers 28 by reaction of Na[(Me 3 Si) 4 Al] with Cp 2 TiCl 2 . Later, Tilley and co-workers prepared Cp 2 M(Cl)SiMe 3 (M = Zr and Hf) 29 reacting Cp 2 MCl 2 with Al(SiMe 3 ) 3 and Cp 2 M(Cl)Si(SiMe 3 ) 3 30 (M = Zr and Hf) utilizing (Me 3 Si) 3 SiLi as nucleophile.…”

Section: Resultsmentioning

confidence: 99%

Tuning the Si–N Interaction in Metalated Oligosilanylsilatranes

et al. 2017

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Most known silatrane chemistry is concerned with examples where the attached silatrane substituent atom is that of an element more electronegative than silicon. The current study features silylated silatranes with a range of electropositive elements attached to the silyl group. The resulting compounds show different degrees of electron density on the silatrane-substituted silicon atom. This directly affects the Si–N interaction of the silatrane which can be monitored either by 29Si NMR spectroscopy or directly by single crystal XRD analysis of the Si–N distance. Within the sample of study the Si–N distance is increased from 2.153 to 3.13 Å. Moreover, the bis(trimethylsilyl)silatranylsilyl unit was studied as a substituent for disilylated germylene adducts.

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“…Among these compounds Cp 2 Ti(Cl)SiMe 3 ( I ), 20 prepared by Rösch et al utilizing the reaction of Cp 2 TiCl 2 with Al(SiMe 3 ) 3 ·Et 2 O, is well characterized with 1 H and 13 C NMR and IR spectra and a low-quality crystal structure ( R = 16%). The titanacyclosilanes Cp 2 Ti(SiPh 2 ) n ( n = 4 ( II ), 5 ( III )) 21−23 were reported as products of the reaction of Cp 2 TiCl 2 with Li(Ph 2 Si) n Li.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Oligosilanyl Compounds of Group 4 Metallocenes with the Oxidation State +3

Arp¹,

Zirngast²,

Marschner³

et al. 2012

Organometallics

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Recently, we showed that titanocene silyls are much more stable with Ti in the oxidation state +3. The current study demonstrates that analogous Zr and Hf compounds can also be obtained by reaction of a suitable metalate precursor with an oligosilanyl dianion. As the obtained complexes formally possess a d1 electron configuration, they were investigated using EPR spectroscopy. The corresponding spectra indicate that the compounds can be considered to also exhibit some cyclosilanyl radical anion character. In order to understand the strong preference of disilylated titan(IV)ocenes for reductive elimination, a theoretical study of the thermodynamics of these reactions was conducted, revealing that this behavior is essentially caused by the weak Si–Ti(IV) bond.

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Synthese und struktur von dicyclopentadienyl(trimethylsilyl)titanchlorid

Cited by 41 publications

References 21 publications

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

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

Tuning the Si–N Interaction in Metalated Oligosilanylsilatranes

Synthesis of Oligosilanyl Compounds of Group 4 Metallocenes with the Oxidation State +3

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