Transition-Metal-Mediated Redistribution at Silicon: A Bimolecular Mechanism Involving Silylene Complexes

Grumbine, Steven K.; Tilley, T. Don

doi:10.1021/ja00094a066

Cited by 37 publications

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“…There do not appear to be any hydrosilation mechanisms in which anion abstraction from silicon is a part of the catalytic cycle, but there is some evidence that such pathways may be involved in silane redistribution reactions. [94] Scheme 46. Generation of catalytically active silylene complexes via anion abstraction from silyl complexes.…”

Section: Overview Of Silylene Complexes: History Bonding and Reactimentioning

confidence: 99%

Electrophilic Activation of Silicon–Hydrogen Bonds in Catalytic Hydrosilations

2017

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Hydrosilation reactions represent an important class of chemical transformations and there has been considerable recent interest in expanding the scope of these reactions by developing new catalysts. A major theme to emerge from these investigations is the development of catalysts with electrophilic character that transfer electrophilicity to silicon via Si-H activation. This type of mechanism has been proposed for catalysts ranging from Group 4 transition metals to Group 15 main group species. Additionally, other electrophilic silicon species, such as silylene complexes and η 3 -H2SiRR' complexes, have been identified as intermediates in hydrosilation reactions. In this Review, different types of catalysts are compared to highlight the range of hydrosilation mechanisms that feature electrophilic silicon centers, and the importance of these catalysts to the development of new hydrosilation reactions is discussed.

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Section: Overview Of Silylene Complexes: History Bonding and Reactimentioning

confidence: 99%

Electrophilic Activation of Silicon–Hydrogen Bonds in Catalytic Hydrosilations

2017

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“…Diese Methode ist zwar zur Bildung katalytisch aktiver Silylenkomplexe genutzt worden (Schema ), aber die Regeneration des Silylen‐Liganden in den Katalysezyklen dieser Hydrosilierungen erfolgte aus Silan durch zwei folgegebundene Si‐H‐Aktivierungen statt einer wiederholten Hydrid‐Abstraktion. Es scheinen keine Hydrosilierungsmechanismen zu existieren, in denen eine Anion‐Abstraktion durch Silicium Teil des Katalysezyklus ist, obgleich es Hinweise gibt, dass solche Reaktionswege für Silan‐Umverteilungsreaktionen bestehen könnten …”

Section: Hydrosilierungen Mittels Elektrophiler Silylenkomplexeunclassified

Elektrophile Aktivierung von Silicium‐Wasserstoff‐ Bindungen in katalytischen Hydrosilierungen

2017

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Hydrosilierungsreaktionen repräsentieren eine wichtige Klasse von chemischen Umwandlungen, und somit besteht ein erhebliches Interesse, den Umfang dieser Reaktionen durch die Entwicklung neuer Katalysatoren zu erweitern. Ein Hauptanliegen, das aus diesen Untersuchungen erwächst, ist die Entwicklung von Katalysatoren mit elektrophilem Charakter, die mittels Si‐H‐Aktivierung die Elektrophilie auf Silicium übertragen. Dieser Mechanismustyp wurde für Katalysatoren vorgeschlagen, die sich von den Übergangsmetallen der 4. Gruppe bis hin zu Hauptgruppenelementverbindungen der 15. Gruppe erstrecken. Zudem sind andere elektrophile Siliciumspezies wie Silylenkomplexe und η3‐H2SiRR′‐Komplexe als Intermediate in Hydrosilierungsreaktionen identifiziert worden. In diesem Aufsatz werden unterschiedliche Typen von Katalysatoren verglichen, um die enorme Breite an Hydrosilierungsmechanismen aufzuzeigen, die über elektrophile Siliciumzentren verlaufen. Die Bedeutung dieser Katalysatoren für die Entwicklung neuer Hydrosilierungsreaktionen wird diskutiert.

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“…Prominent examples include the formation of base-stabilized silylenes [54–55], insertion of olefins into hydrosilylenes [56], and bimolecular redistribution of thiolates between ruthenium silyl and silylene complexes [57]. Reactivity that involves metal-ligand cooperation (in the sense described in this article) has been reported in the formal [2 + 2] cycloaddition of isocyanates to ruthenium(II) silylenes [58] (Scheme 8).…”

Section: Reviewmentioning

confidence: 99%

Metal–ligand multiple bonds as frustrated Lewis pairs for C–H functionalization

Whited¹

2012

Beilstein J. Org. Chem.

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SummaryThe concept of frustrated Lewis pairs (FLPs) has received considerable attention of late, and numerous reports have demonstrated the power of non- or weakly interacting Lewis acid–base pairs for the cooperative activation of small molecules. Although most studies have focused on the use of organic or main-group FLPs that utilize steric encumbrance to prevent adduct formation, a related strategy can be envisioned for both organic and inorganic complexes, in which "electronic frustration" engenders reactivity consistent with both nucleophilic (basic) and electrophilic (acidic) character. Here we propose that such a description is consistent with the behavior of many coordinatively unsaturated transition-metal species featuring metal–ligand multiple bonds, and we further demonstrate that the resultant reactivity may be a powerful tool for the functionalization of C–H and E–H bonds.

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Transition-Metal-Mediated Redistribution at Silicon: A Bimolecular Mechanism Involving Silylene Complexes

Cited by 37 publications

References 0 publications

Electrophilic Activation of Silicon–Hydrogen Bonds in Catalytic Hydrosilations

Electrophilic Activation of Silicon–Hydrogen Bonds in Catalytic Hydrosilations

Elektrophile Aktivierung von Silicium‐Wasserstoff‐ Bindungen in katalytischen Hydrosilierungen

Metal–ligand multiple bonds as frustrated Lewis pairs for C–H functionalization

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