Base-Free Silylene Complexes without .pi.-Donor Stabilization. Molecular Structure of [Cp*(PMe3)2Ru:SiMe2][B(C6F5)4]

Grumbine, Steven K.; Tilley, T. Don; Arnold, Frederick P.; Rheingold, Arnold L.

doi:10.1021/ja00091a074

Cited by 119 publications

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“…[413,414] Theh ydrosilylation of unsaturated functional groups has received much attention, and the Chalk-Harrod-type mechanism for the hydrosilylation reactivity of platinum-and rhodium-based catalysts has been well-documented for many years. [416][417][418][419] WCA ] À )f eaturing aS i ÀH bond have been shown to be capable of the hydrosilylation of alkenes through an unusual mechanism. [416][417][418][419] WCA ] À )f eaturing aS i ÀH bond have been shown to be capable of the hydrosilylation of alkenes through an unusual mechanism.…”

Section: Asymmetric Hydrogenation and Hydrosilylation Reactionsmentioning

confidence: 99%

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

et al. 2018

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This Review gives a comprehensive overview of the most topical weakly coordinating anions (WCAs) and contains information on WCA design, stability, and applications. As an update to the 2004 review, developments in common classes of WCA are included. Methods for the incorporation of WCAs into a given system are discussed and advice given on how to best choose a method for the introduction of a particular WCA. A series of starting materials for a large number of WCA precursors and references are tabulated as a useful resource when looking for procedures to prepare WCAs. Furthermore, a collection of scales that allow the performance of a WCA, or its underlying Lewis acid, to be judged is collated with some advice on how to use them. The examples chosen to illustrate WCA developments are taken from a broad selection of topics where WCAs play a role. In addition a section focusing on transition metal and catalysis applications as well as supporting electrolytes is also included.

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Section: Asymmetric Hydrogenation and Hydrosilylation Reactionsmentioning

confidence: 99%

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

et al. 2018

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“…For this reason it seems to be interesting to elucidate the possibility of the presence of Pt-E dppp interactions. A comparison could be drawn to the isovalence electronic platinum silylene complex fragment [(PCy 3 ) 2 (H)Pt@Si(SEt) 2 ] + reported by Tilley and co-workers [22,23] some time ago with an as well nearly orthogonal arrangement of the Si(SR) 2 and the L 3 Pt plane. Theoretical calculations on the basis of this system reveal a good overlap of the Si p orbital and the Pt orbitals of suitable symmetry.…”

Section: Theoretical Calculations On the Model Compound {(Dhpe)-pt[gamentioning

confidence: 99%

The reaction of the group-13 alkyls ER3 (E=Al, Ga, In; R=CH2t-Bu, CH2 SiMe3) with the platinum-complex [(dcpe)Pt(H)(CH2t-Bu)]

Fischer

Weiß

Winter

et al. 2004

Journal of Organometallic Chemistry

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“…The challenge to realize metallasilabenzene could be attributed to the weak MSi bond caused by the low electronegativity of silicon, as the first X‐ray structure of a base‐stabilized transition metal silylene complex was not synthesized until 198711 although an intermediate was reported as early as 1970 12. Despite that the synthesis of silylene complexes benefits from the stabilization of Lewis base, the base‐free silylene complexes were synthesized in 1994 13. Among these silylene complexes, high reactivities were exhibited toward nucleophiles, such as water, alcohols, ketones, isocyanates, and phosphorus ylides owing to the polarization of the metal‐silicon bond,14 which could be attributed to the fact that silicon is reluctant to participate in π bonding 15…”

Section: Introductionmentioning

confidence: 99%

Unexpected 1,2‐Migration in Metallasilabenzenes: Theoretical Evidence for Reluctance of Silicon to Participate in π Bonding

Huang

Zhu

2014

Chemistry An Asian Journal

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Density functional theory (DFT) calculations were carried out to investigate the 1,2-migration in metallasilabenzenes. The results suggested that the chloride migration of metallabenzenes is unfavorable due to the loss of aromaticity in the nonaromatic analogues. In sharp contrast, such a migration in metallasilabenzenes is favorable due to the reluctance of silicon to participate in π bonding. The migration of hydride and methyl group from the metal center to the silicon atom in metallasilabenzenes is computed to be also feasible. In addition, the π donor ligand and the third row transition metal can stabilize metallasilabenzenes. Thus, such a migration becomes less favorable thermodynamically and kinetically. These findings could be very helpful for synthetic chemists to realize the first metallasilabenzene.

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Base-Free Silylene Complexes without .pi.-Donor Stabilization. Molecular Structure of [Cp*(PMe3)2Ru:SiMe2][B(C6F5)4]

Cited by 119 publications

References 0 publications

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

The reaction of the group-13 alkyls ER3 (E=Al, Ga, In; R=CH2t-Bu, CH2 SiMe3) with the platinum-complex [(dcpe)Pt(H)(CH2t-Bu)]

Unexpected 1,2‐Migration in Metallasilabenzenes: Theoretical Evidence for Reluctance of Silicon to Participate in π Bonding

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