Synthetic, structural and reactivity studies with new group 4 transition-metal silyl complexes

Imori, Toru; Heyn, Richard H.; Tilley, T. Don; Rheingold, Arnold L.

doi:10.1016/0022-328x(94)05336-a

Cited by 32 publications

(23 citation statements)

References 16 publications

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“…The solid state structure of 7 (Figure ), which crystallizes in the triclinic space-group P 1̅ with two crystallographically independent molecules in the asymmetric unit was determined. The Si–Zr distance of 2.799(1)/2.803(1) Å is close to that of related oligosilanyl Zr(X)Cp 2 (X = Cl, Br) compounds, − and the Si–F bond length is close to that of 3a . The Zr–Si–Si–F torsional angles of the two independent molecules of 7 are 145.6 and 162.56, indicating a transoid arrangement with no direct interaction between F and Zr.…”

Section: Resultsmentioning

confidence: 99%

Disilene Fluoride Adducts versus β-Halooligosilanides

et al. 2019

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Extending the chemistry of disilene fluoride adducts studied earlier by us, we investigated the formation of 1,1-bis(trimethylsilyl)fluorodiphenylsilylsilanide, which was prepared by reaction of (Me 3 Si) 3 SiSiPh 2 F with KO t Bu. The formed FPh 2 SiSi(Me 3 Si) 2 K displays distinctively different structural and spectroscopic features compared to the earlier reported F(Me 3 Si) 2 SiSi(SiMe 3 ) 2 K. While the latter eliminates metal fluoride upon reaction with MgBr 2 , the respective magnesium silanide is formed from FPh 2 SiSi(Me 3 Si) 2 K. Reaction of (Me 3 Si) 3 SiSiPh 2 Cl with KO t Bu proceeded similarly, but the formed ClPh 2 SiSi(Me 3 Si) 2 K easily undergoes potassium chloride elimination to the disilene Ph 2 SiSi(SiMe 3 ) 2 . Compared to F(Me 3 Si) 2 SiSi(SiMe 3 ) 2 K, which can be regarded as a disilene fluoride adduct, structural, spectroscopic, and reactivity properties of FPh 2 SiSi(Me 3 Si) 2 K distinguish it as a β-fluorodisilanide.

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Section: Resultsmentioning

confidence: 99%

Disilene Fluoride Adducts versus β-Halooligosilanides

et al. 2019

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“…(SiMe 3 ) 3 ]Cl (10), respectively, in dehydrocondensation of phenylsilane and dibutylstannane were studied. 143 According to the data of GLC-mass spectrometry, a viscous mixture of linear H(PhHSi) n H and cyclic (PhSiH) n (n = 5 or 6) oligomers (M n = 900, M w = 1810) was formed from phenylsilane in the presence of the complex 9 after 24 h. Under analogous conditions, a mixture of linear and cyclic polysilanes with M n = 1870 and M w = 3280 was formed upon catalysis by the CpCp*Zr[Si(SiMe 3 ) 3 ]Cl complex, which does not contain the trimethylsilyl group in the cyclopentadienyl ring. Dehydrocondensation of dibutylstannane in the presence of the complex 9 affords polybutylstannanes with a broad molecular weight distribution spectrum (M w = 4800, M n = 1420).…”

Section: Mec (Co)6co2mentioning

confidence: 99%

Dehydrocondensation of organylsilanes giving Si–Si bonds

Pukhnarevich¹,

Воронков²,

Kopylova³

2000

Russ. Chem. Rev.

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Particle trapping effects on stimulated Brillouin and Raman scattering have been investigated. A time and space dependent model assumes a Maxwellian plasma which is taken to be homogeneous in the interaction region. Ion trapping has a rather weak effect on stimulated Brillouin scattering and large reflectivities are obtained even in strong trapping regime. Stimulated Raman scattering is considerably reduced by electron trapping. Typically 15-20 times larger laser intensities are required to obtain same reflectivity levels than without trapping.

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“…Investigations on the chemistry of group 4 silyl complexes were started in the late 1960s, with some work on silyl titanium chemistry − and Lappert’s contributions of zirconocene and hafnocene complexes. − Systematic studies of zirconocene and hafnocene silyl complexes were carried out by Tilley and co-workers, − who especially studied aspects of σ-bond metathesis and the catalytic dehydrocoupling polymerization of hydrosilanes catalyzed by these compounds. − While in the initial papers by Harrod and co-workers − on the dehydrocoupling polymerization of hydrosilanes titanium was acting as the catalytically active element, Tilley’s mechanistic studies were carried out using hafnium or zirconium. Starting out from CpCp*M(Cl)Si(SiMe 3 ) 3 (M = Zr, Hf) it was shown that σ-bond metathesis reaction with a hydrosilane leads to (Me 3 Si) 3 SiH and a new metal silyl complex, which in reaction with another hydrosilane forms a disilane and a metal hydride …”

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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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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Synthetic, structural and reactivity studies with new group 4 transition-metal silyl complexes

Cited by 32 publications

References 16 publications

Disilene Fluoride Adducts versus β-Halooligosilanides

Disilene Fluoride Adducts versus β-Halooligosilanides

Dehydrocondensation of organylsilanes giving Si–Si bonds

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

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