Novel trans-.eta.2-Alkyne Complexes of Titanocene with Strong Si-H-Ti Interactions. Synthesis, Spectral Characteristics, and x-ray Crystal Structure

Ohff, Andreas; Kosse, P.; Baumann, Wolfgang; Tillack, Annegret; Kempe, Rhett; Goerls, Helmar; Burlakov, Vladimir V.; Rosenthal, Uwe

doi:10.1021/ja00146a032

Cited by 70 publications

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“…The reduction of [L 2 TiCl 2 ] with equimolar amounts of magnesium in THF in the presence of the alkynylsilanes provides their complexes in high purity and yields (Scheme 2 (14), wobei die Bildung der unsymmetrisch substituierten Verbindungen 13 a, 14 a kinetisch begüstigt ist und zuerst erfolgt. Eine anschlieûende Cycloreversion führt zu den thermodynamisch stabileren und symmetrisch substituierten Metallacyclopentadienen 13 b und 14 b. Beide Verbindungen zeigen keine Wechselwirkung der Si-H-Gruppen mit dem Metall.…”

Section: Resultsunclassified

“…This shift is difficult to rationalize, but an important contribution might be made by the unusual coordination geometry around this quaternary carbon atom. The bond angle Si-C-C is only 1508, [14] and it is possible to define a plane through the carbon in such a way that all atomic neighbors reside on the same side of this plane. In other words, the side opposite the titanium is completely naked.…”

Section: Resultsmentioning

confidence: 99%

“…[13] Recently, we reported the reaction of the cis-alkyne complex [Cp 2 Ti(h 2 -Me 3 SiC 2 SiMe 3 )] with tBuCCSiMe 2 H which gave the trans-alkyne complex [Cp 2 Ti-(tBuCCSiMe 2 H)] with a strong Si-H-Ti interaction. [14] Ab initio calculations on this complex suggest a better formulation as a d 2 metal compound with a strong s*-accepting H ± Si bond. [15] In catalytic investigations titanocene alkyne complexes [L 2 Ti(h 2 were found to be effective precatalysts in dehydrogenative silane polymerization.…”

Section: Introductionmentioning

confidence: 94%

“…Crystallographic characterization: In addition to the already crystallographically characterized titanium complex 1, [14] we obtained suitable single crystals of the solvent-free zirconium complex 12 b (Table 4). The structure determined (Figure 2) enabled the two metallocenes with different central metals to be compared with regard to the silicon-hydrogen-metal interaction, because the interacting hydrogen atom could be found and refined.…”

Section: Dynamic Behavior and Temperature Dependence In Solutionmentioning

confidence: 99%

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Si-H Activation in Titanocene and Zirconocene Complexes of Alkynylsilanes RC≡CSiMe2H (R=tBu, Ph, SiMe3, SiMe2H): A Model To Understand Catalytic Reactions of Hydrosilanes

et al. 1998

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An agostic interaction between the Si–H bond and the metal center (depicted on the right) is the characteristic feature of the title complexes, which could be prepared by acetylene exchange reactions. IR, NMR, and X‐ray structural investigations reveal that the effect of the Si‐H‐metal interaction is considerably stronger at low temperatures and in the solid state. This mode of bond activation is important in active catalysts for hydrosilylation and dehydrogenative polysilane reactions.

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Section: Resultsunclassified

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 94%

Section: Dynamic Behavior and Temperature Dependence In Solutionmentioning

confidence: 99%

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Si-H Activation in Titanocene and Zirconocene Complexes of Alkynylsilanes RC≡CSiMe2H (R=tBu, Ph, SiMe3, SiMe2H): A Model To Understand Catalytic Reactions of Hydrosilanes

et al. 1998

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“…zirconium complexes of alkynylsilanes 46 (M=Ti, R='Bu[76]; M=Zr, R=Me 3 Si[77]) containing Si(H)Me 2 group display unusual structure. The substitution of one methyl group at the silicon atom in ferf-butyl(trimethylsilyl)acetylene complex of titanocene by a hydrogen atom gives the bend of the silyl group in the opposite direction, to a transconfiguration…”

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MOLECULAR STRUCTURE OF ORGANOSILICON COMPOUNDS WITH Si-M (M = Ge, Sn, Pb, Ti, Zr, Hf) BONDS

Lukevics¹,

Pudova²

1999

Main Group Metal Chemistry

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The results of the structural investigations of the group 4 metal derivatives containing direct Si-Ge, Si-Sn, Si-Pb, Si-Ti, Si-Zr, Si-Hf bonds are summarized in the present review. IntroductionRecently we have published a comprehensive survey of data on the molecular structure of organosilicon compounds with silicon-silicon bonds [1], as a part of the structural investigations related to the silyl derivatives of the group 4 elements with Si-M bonds. Herein, we present a review concerning the molecular structure of germanium, tin, lead, titanium, zirconium, hafnium derivatives bearing silyl substituents at the metal atoms. Only a few structures with direct Si-M (M=Ge, Sn, Pb, Ti, Zr, Hf) bonds were studied 10 years ago. Now the interest in this area is becoming increasingly prominent and exciting progress has been made in the chemistry and structural characterization of silyl derivatives of group 4 metals.

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Transition‐Metal Silyl Complexes

Eisen¹

2009

Patai's Chemistry of Functional Groups

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Introduction Group‐3 Silyl Complexes Lanthanide Silyl Derivatives Group‐4 Silyl Complexes Actinide Silyl Complexes Group‐5 Silyl Complexes General Introduction to Late‐Transition‐Metal Silicon‐Containing Complexes Group‐6 Silylene Complexes Group‐6 Silyl Complexes Group‐7 Silylene Complexes Group‐7 Silyl Derivatives Group‐8 Silyl Derivatives Group‐9 Silicon‐Containing Complexes Group‐10 Silicon‐Containing Complexes Copper and Mercury Silyl Complexes Acknowledgments

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Novel trans-.eta.2-Alkyne Complexes of Titanocene with Strong Si-H-Ti Interactions. Synthesis, Spectral Characteristics, and x-ray Crystal Structure

Cited by 70 publications

References 0 publications

Si-H Activation in Titanocene and Zirconocene Complexes of Alkynylsilanes RC≡CSiMe2H (R=tBu, Ph, SiMe3, SiMe2H): A Model To Understand Catalytic Reactions of Hydrosilanes

Si-H Activation in Titanocene and Zirconocene Complexes of Alkynylsilanes RC≡CSiMe2H (R=tBu, Ph, SiMe3, SiMe2H): A Model To Understand Catalytic Reactions of Hydrosilanes

MOLECULAR STRUCTURE OF ORGANOSILICON COMPOUNDS WITH Si-M (M = Ge, Sn, Pb, Ti, Zr, Hf) BONDS

Transition‐Metal Silyl Complexes

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