Reactivity of silylene complexes

Okazaki, Masanori; Tobita, Hiromi; Ogino, Hiroshi

doi:10.1039/b210588h

Cited by 237 publications

(112 citation statements)

References 72 publications

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“…For example, transition metal silylene complexes bind and activate substrates at the metal-bound silicon center, which has Lewis acidic character (Scheme 2, B). [15][16] In these reactions, a metal-silicon bond is preserved upon binding of the substrate, but the resulting adduct possesses a silicon center that is 4-coordinate rather than 5-coordinate. However, more recently reported hydrosilation mechanisms do invoke the formation of intermediates in which the substrate binds to a 5-or 6-coordinate silicon center (Scheme 2, C).…”

Section: Summary and Outlook 31mentioning

confidence: 99%

“…Terminal silylene ligands usually exhibit Lewis acidity at silicon (Scheme 45), and this property features heavily in the reactivity of most silylene complexes. [15,16,82] A wide range of nucleophilic substrates (e.g. water, [83] alcohols, [84] ketones, [85] isocyanates, [86] olefins, [87] nitriles, [88] isocyanides [89] ) undergo activation by the highly electrophilic silicon center of these complexes.…”

Section: Overview Of Silylene Complexes: History Bonding and Reactimentioning

confidence: 99%

“…Rochow's Direct Process, [90] Si-Si bond formation [91] ), as well as from fundamental interest in examining heavy analogues of carbene complexes. A variety of methods have been developed for preparing isolable silylene complexes, [15,16] and it has subsequently been discovered that many of these species participate in stoichiometric and catalytic hydrosilations. [85e,f;87a,c,d] The focus on studying isolated and well-characterized silylene complexes may contribute to the tendency to observe their involvement in stoichiometric transformations rather than catalytic reactions.…”

Section: Overview Of Silylene Complexes: History Bonding and Reactimentioning

confidence: 99%

“…This review will examine hydrosilation catalysts for which the generation of an electrophilic silicon center is key to the activation of the unsaturated substrate. [13][14][15][16] These types of mechanisms were first proposed in the 1990's and a range of…”

Section: Introductionmentioning

confidence: 99%

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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: Summary and Outlook 31mentioning

confidence: 99%

Section: Overview Of Silylene Complexes: History Bonding and Reactimentioning

confidence: 99%

Section: Overview Of Silylene Complexes: History Bonding and Reactimentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electrophilic Activation of Silicon–Hydrogen Bonds in Catalytic Hydrosilations

2017

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“…[36] Tr ansition-metal complexes of silyenes are also know to react in such amanner. [42] Additionally,Bercaw and Hillhouse have reported the related Group 4c omplexes [{Cp* 2 M(H)} 2 m-O] (M = Zr and Hf;C p* = pentamethylcyclopentadienyl), formed via s-bond metathesis pathways. [10] It is worth noting at this stage that 2 does not react further with 1 to afford the related imide-bridged species.…”

Section: Methodsmentioning

confidence: 99%

E–H Bond Activation of Ammonia and Water by a Geometrically Constrained Phosphorus(III) Compound

et al. 2015

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The synthesis of ap hosphorus(III) compound bearing aN ,N-bis(3,5-di-tert-butyl-2-phenoxy)amide ligand is reported. This species has been found to react with ammonia and water,a ctivating the EÀHb onds in both substrates by formal oxidative addition to affordt he corresponding phosphorus(V) compounds.I nt he case of water,b oth O À H bonds can be activated, splitting the molecule into its constituent elements.T oo ur knowledge,t his is the first example of ac ompound based on main group elements that sequentially activates water in this manner.

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Silicon: Inorganic Chemistry

Lickiss

2005

Encyclopedia of Inorganic Chemistry

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Silicon is an element of vital importance in many areas of modern synthetic chemistry, the electronics industry and in materials science. This article attempts to summarize the many types of important inorganic derivatives of silicon but excludes the chemistry of silicates and zeolites, which are covered in separate articles. The isolation of elemental silicon from sand is described together with the various methods of purification of the element for use in the semiconductor industry. A brief description of the occurrence of silicon in biology is also given. The bulk of the article deals with compounds of silicon organized according to coordination number. One‐coordinate compounds are short‐lived intermediates and are described briefly. Two‐coordinate compounds, silylenes, have become increasingly important in recent years as are transition metal complexes in which they act as ligands. The use of bulky substituents has allowed stable silylenes to be isolated and their chemistry is described. Three‐coordinate compounds comprise radicals, cations, anions, and silanes (compounds containing a double bond to Si). These species are also generally short‐lived and reactive. The bulk of the article deals with four‐coordinate compounds and is organized according to the substituents at silicon. The industrially important hydrosilanes and halosilanes are described together with the mixed halohydrosilanes and the less common pseudohalosilanes. Alkoxysilanes are also industrially important and these are discussed with other oxygen derivatives such as esters and silanols. Compounds containing SiN bonds are also common and have interesting structural features. The preparation and structures of transition metal complexes containing silyl ligands is described. This is followed by a description of compounds containing silicon with coordination number five or six. The final section describes the analytical methods for the determination of the composition and structure of inorganic silicon compounds. Compounds containing SiC bonds are excluded throughout.

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Reactivity of silylene complexes

Cited by 237 publications

References 72 publications

Electrophilic Activation of Silicon–Hydrogen Bonds in Catalytic Hydrosilations

Electrophilic Activation of Silicon–Hydrogen Bonds in Catalytic Hydrosilations

E–H Bond Activation of Ammonia and Water by a Geometrically Constrained Phosphorus(III) Compound

Silicon: Inorganic Chemistry

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