Reactions of Hydrosilanes with Transition-Metal Complexes:  Formation of Stable Transition-Metal Silyl Compounds

Corey, Joyce Y.; Braddock‐Wilking, Janet

doi:10.1021/cr9701086

Cited by 696 publications

(562 citation statements)

References 569 publications

(1,342 reference statements)

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“…3d); this explains the dihedral angle between Pd 7 sheets I and II of 37.7°. The Si(3)-Pd(11) bond distance of 2.477(3) Å is longer than that found in common Pd-Si complexes (around 2.3-2.4 Å) 32,33 , but shorter than several Pd-Si bonds seen in Osakada's planar Pd 4 Si 3 cluster (2.5052(8)-2.5456(7) Å) 28 . Similarly, the interplane bonding of Si(3) in sheet III and Pd (11) in sheet IV is the origin of the dihedral angle of 47.7°.…”

Section: Synthesis Of Folding Pd 11 Nanosheet 2 Insertion Of a Pd(cnr)mentioning

confidence: 63%

A ladder polysilane as a template for folding palladium nanosheets

et al. 2013

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Although discrete nano-sized compounds consisting of a monolayer sheet of multiple atoms have attracted much attention, monolayer transition metal nanosheets are difficult to access. Here we report a template synthesis of the folding metal nanosheet (2) consisting of 11 palladium atoms by treatment of a ladder polysilane, decaisopropylbicyclo[2.2.0]hexasilane (1), with Pd(CN t Bu) 2 . Crystallographic analysis reveals that the compound is composed of two monolayer Pd 7 sheets sharing three palladium atoms at the junction. Each Pd atom is stabilized by Pd-Si s-bonds, Pd-Pd bonds and coordination of isocyanides. Ligand exchange of 2 from CN t Bu to CN(2,4,6-Me 3 -C 6 H 2 ) is accompanied by structural rearrangement, leading to the formation of another folding Pd 11 nanosheet (3) consisting of two edge-sharing Pd 7 sheets. The shapes of the Pd 7 sheets as well as the dihedral angle between the two Pd 7 sheets are dependent on the substituent of the isocyanide ligand.

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Section: Synthesis Of Folding Pd 11 Nanosheet 2 Insertion Of a Pd(cnr)mentioning

confidence: 63%

A ladder polysilane as a template for folding palladium nanosheets

et al. 2013

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“…An expansion of this signal to render the 29 Si satellites visible shows clearly that, as the temperature is lowered and the equilibrium shifts towards 2, the value for the 1 JSi-H coupling constant drops smoothly from 177 Hz in free Et3Si-H to a value of 107(2) Hz at 213 K (Fig 3b). A lowering of this coupling constant would be expected 46 as the Si-H bond weakens upon interaction with the boron center. It was also anticipated that the stretching frequency of the Si-H bond would be impacted upon adduct Fig.…”

Section: Resultsmentioning

confidence: 99%

Direct observation of a borane–silane complex involved in frustrated Lewis-pair-mediated hydrosilylations

et al. 2014

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“…Thus, it is notable that an adduct between triethylsilane and 1,2,3-tris(pentafluorophenyl)-4,5,6,7-tetrafluoro-1-boraindene (2) was recently characterized in solution and in the solid state (Scheme 6). [27] [36] and B-H distances of perfluorohydridoborate anions are 1.14 Å [37] Although hydrosilation studies were not reported for 2, initial indications are that the coordinated silane is electrophilic. Adduct 2•HSiEt3 reacted with bis(triphenylphosphine)iminium chloride, [PPN][Cl], to form a hydridoborate compound by Si-H cleavage and formation of Et3Si-Cl (Scheme 7).…”

Section: Reviewmentioning

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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Reactions of Hydrosilanes with Transition-Metal Complexes: Formation of Stable Transition-Metal Silyl Compounds

Cited by 696 publications

References 569 publications

A ladder polysilane as a template for folding palladium nanosheets

A ladder polysilane as a template for folding palladium nanosheets

Direct observation of a borane–silane complex involved in frustrated Lewis-pair-mediated hydrosilylations

Electrophilic Activation of Silicon–Hydrogen Bonds in Catalytic Hydrosilations

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