Making and Breaking of SiE (E = C, Si) Bonds by Oxidative Addition and Reductive Elimination Reactions

Schubert, Ulrich

doi:10.1002/anie.199404191

Cited by 66 publications

(13 citation statements)

References 29 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As mentioned above, Schubert stated that the energy released when a Si-Si bond is broken is greater the energy released when breaking a Si-C bond. [3] Grunenberg also reported a higher Si-Si bond energy than Si-C bond energy. [43] These arguments agree with the trend seen in Table 3.…”

Section: Linear Oxidation Kineticsmentioning

confidence: 99%

“…Deal and Grove attributed the activation energy for the Si oxidation linear reaction rate to the breaking of Si-Si bonds. [3] The activation energy for linear oxidation kinetics of SiC should therefore be smaller than that of Si oxidation based on bond breaking considerations. [3] The activation energy for linear oxidation kinetics of SiC should therefore be smaller than that of Si oxidation based on bond breaking considerations.…”

Section: Introductionmentioning

confidence: 99%

“…[1] Schubert states that the energy required to break a Si-Si bond is greater than the energy to break a Si-C bond. [3] The activation energy for linear oxidation kinetics of SiC should therefore be smaller than that of Si oxidation based on bond breaking considerations. The temperature dependence of the parabolic rate constant reflects the enthalpy for the transport of oxidant through the growing SiO 2 scale and is expected to be the same for silicon and silicon carbide.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

A Review of SiC Fiber Oxidation with a New Study of Hi‐Nicalon SiC Fiber Oxidation

Wilson

Opila

2016

Adv Eng Mater

View full text Add to dashboard Cite

The linear and parabolic oxidation rate constants and activation energies for SiC fibers available in the literature are reviewed for the first time. Oxidation experiments are also conducted with Hi-Nicalon SiC fibers over 700-1 300 C in dry O 2 with thermogravimetric analysis. Linear oxidation kinetics are observed from 700 to 800 C and parabolic kinetics are observed from 900 to 1 300 C. The linear and parabolic oxidation rate constant activation energies are determined to be 83 and 108 kJ mol À1 , respectively. These kinetic results are compared with the literature values. Differences in oxidation behavior are assessed as a function of fiber composition.

show abstract

Section: Linear Oxidation Kineticsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

A Review of SiC Fiber Oxidation with a New Study of Hi‐Nicalon SiC Fiber Oxidation

Wilson

Opila

2016

Adv Eng Mater

View full text Add to dashboard Cite

show abstract

“…Hydrosilylation processes of olefins and acetylenes, which are frequently catalyzed by Pt complexes, are thought to proceed by the Chalk−Harrod mechanism which invokes C−Si bond formation as the product-forming step . Reactions of metal alkyl complexes with primary silanes can lead to products of both C−H and C−Si reductive elimination. ,, For instance, reaction of (dmpe)Pt(Me)(OTf) (dmpe = Me 2 PCH 2 CH 2 PMe 2 ) with Et 3 SiH led to formation of CH 4 and CH 3 SiEt 3 5a. Methane was formed in the reaction of MeRh(PMe 3 ) 4 with HSiPh 3 ,5b while, in the analogous reaction with HSiEt 3 , both methane and CH 3 SiEt 3 were formed.…”

Section: Introductionmentioning

confidence: 99%

Exclusive C−Si Bond Formation upon Reaction of a Platinum(II) Alkyl with Silanes

1998

View full text Add to dashboard Cite

An unusual, highly selective C−Si coupling reaction takes place upon treating the platinum(II) alkyl complex cis-(DIPPIDH)(DIPPID)PtMe (2) (DIPPIDH = α2-(diisopropylphosphino)isodurene, 1) with HSiR3 (R3 = Et3, EtMe2, Me2Ph), leading to formation of MeSiR3 and the hydrido complex trans-(DIPPIDH)(DIPPID)PtH (5). The overall process involves activation of a Si−H bond, reverse-cyclometalation of the phosphine ligand DIPPIDH (1), and C−Si elimination. The resulting thermally stable platinum(II) hydride complex 5 was independently prepared by thermolysis of a platinum(II) dihydride, trans-(DIPPIDH)2PtH2 (6), which was obtained by reaction of 2 with H2. In the absence of silane, the cis complex 2 isomerizes thermally to trans-(DIPPIDH)(DIPPID)PtMe (3), which does not react productively with silanes. Our results indicate that opening of the metallacycle of 2 by benzylic C−H formation is kinetically preferred over formation of CH4 or CH3SiR3.

show abstract

“…Introduction of electropositive elements such as group 14 metals instead of electronegative elements into organic macrocycles with appropriate arrangement may lead to the development of new functional molecules. Especially, in view of the intriguing chemical and physical properties of Si−Si σ-bonds, an efficient synthesis of macrocycles with regularly arranged Si−Si bonds may be desired. Palladium-catalyzed Si−Si σ-bond metathesis of cyclic disilanes seemed to provide a convenient method for preparation of macrocycles containing Si−Si bonds in the ring.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Organosilicon Macrocycles. Palladium-Catalyzed Ring-Enlargement Oligomerization of Cyclic Disilanes via Si−Si σ-Bond Metathesis

et al. 1996

View full text Add to dashboard Cite

Bis(tert-alkyl isocyanide)palladium(0) complexes catalyzed a ring-enlargement oligomerization of 1,1,2,2-tetramethyl-1,2-disilacyclopentane through Si−Si σ-bond metathesis to give cyclic oligomers up to the 40-membered octamer. The cyclic structure of the tetramer was established by the single-crystal X-ray diffraction method, which showed that the four Si−Si bonds of the tetramer were in a close to parallel arrangement. Reactivities of the dimer, trimer, and tetramer in the presence of bis(tert-butyl isocyanide)palladium(0) revealed that the present Si−Si σ-bond metathesis proceeded reversibly, in which the −Me2Si(CH2)3SiMe2− unit of the disilacyclopentane was successively inserted into the Si−Si bond of the oligomer to give higher oligomers. The intermediary 6-membered bis(organosilyl)bis(tert-alkyl isocyanide)palladium complex, which arose from oxidative addition of the disilacyclopentane onto bis(tert-alkyl isocyanide)palladium(0), was isolated and characterized by the single-crystal X-ray method. The insertion of the −Me2Si(CH2)3SiMe2− unit also occurred with linear disilanes and digermane to give linear oligomers. The cyclic trimer and tetramer reacted with 2,6-diisopropylphenyl isocyanide in the presence of Pd(OAc)2 to afford an 18-membered-ring triimine and 24-membered-ring tetraimine, respectively, in which the isocyanides were inserted into all the Si−Si linkages. Oxidation of the cyclic oligomers with trimethylamine oxide gave the corresponding cyclic oligo(disiloxane) species in quantitative yields. Unexpected polymerization of the disilacyclopentane occurred in the presence of the (η5-cyclopentadienyl)(η3-allyl)palladium(II) catalyst to give poly(Me2Si(CH2)3SiMe2) compounds with high molecular weights.

show abstract

Making and Breaking of SiE (E = C, Si) Bonds by Oxidative Addition and Reductive Elimination Reactions

Cited by 66 publications

References 29 publications

A Review of SiC Fiber Oxidation with a New Study of Hi‐Nicalon SiC Fiber Oxidation

A Review of SiC Fiber Oxidation with a New Study of Hi‐Nicalon SiC Fiber Oxidation

Exclusive C−Si Bond Formation upon Reaction of a Platinum(II) Alkyl with Silanes

Synthesis of Organosilicon Macrocycles. Palladium-Catalyzed Ring-Enlargement Oligomerization of Cyclic Disilanes via Si−Si σ-Bond Metathesis

Contact Info

Product

Resources

About