Synthesis and Reactivity of Functionalized Silicon(II) Compounds: Iminosilylene, Phosphinosilylene, Hydrosilylene, and Related Compounds

Bag, Prasenjit; Ahmad, Syed Usman; Inoue, Shigeyoshi

doi:10.1246/bcsj.20160284

Cited by 26 publications

(8 citation statements)

References 155 publications

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“…Theoretical calculations revealed a diffusion over the carbene moieties for the HOMO (lone pair orbital at Si) as well as the LUMO. Because the reactivity of both NHC-stabilized arylchlorosilyliumylidene ions 588a and 588b was recently summarized in a mini-review by us, 672 only a brief recap is given here.…”

Section: Chemical Reviewsmentioning

confidence: 99%

NHCs in Main Group Chemistry

et al. 2018

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Since the discovery of the first stable N-heterocyclic carbene (NHC) in the beginning of the 1990s, these divalent carbon species have become a common and available class of compounds, which have found numerous applications in academic and industrial research. Their important role as two-electron donor ligands, especially in transition metal chemistry and catalysis, is difficult to overestimate. In the past decade, there has been tremendous research attention given to the chemistry of low-coordinate main group element compounds. Significant progress has been achieved in stabilization and isolation of such species as Lewis acid/base adducts with highly tunable NHC ligands. This has allowed investigation of numerous novel types of compounds with unique electronic structures and opened new opportunities in the rational design of novel organic catalysts and materials. This Review gives a general overview of this research, basic synthetic approaches, key features of NHC-main group element adducts, and might be useful for the broad research community.

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Section: Chemical Reviewsmentioning

confidence: 99%

NHCs in Main Group Chemistry

et al. 2018

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“…In this context, the recently synthesized germylenes A – D are important examples for the creative use of substituent effects to modify and control the reactivity of germylenes (Chart ). On the other hand, silylenes and germylenes have been used as ligands in transition-metal complexes . Compared to the widespread use of carbenes as substituents in organometallic compounds, this chemistry is still in its infancy.…”

Section: Introductionmentioning

confidence: 99%

Hafnocene-based Bicyclo[2.1.1]hexene Germylenes – Formation, Reactivity, and Structural Flexibility

et al. 2018

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2,5-Disilylsubstituted germole dianions 1 react with hafnocene dichloride to give hafnocene-based bicyclo[2.1.1]hexene germylenes 3. Their formation proceeds via hafnocene-germylene complexes 2 that were identified by NMR and UV spectroscopy. Germylenes 3 are stabilized by homoconjugation between the empty 4p(Ge) orbital and the π-bond of the innercyclic C═C double bond. This interaction can be understood as σ, π-coordination of the butadiene part to the dicoordinated germanium atom that leaves the 16e hafnocene moiety electronically unsaturated. We demonstrate that this new class of germylenes might serve as ligand to a variety of low-valent transition-metal complexes. The structure of the germylene ligand in complexes with Fe(0), Ni(0), and Au(I) and in reaction products with N-heterocyclic carbenes showed an intriguing structural flexibility that allows to accommodate different electronic situations at the ligating germanium atom. The origin of this structural adaptability is the interplay between the topological flexible unsaturated germanium ring and the hafnocene group.

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“…Nanoarchitectonics may be a good navigator for evolution from materials to life activities 117 as well as design and constructions of highly advanced bioactive functional materials systems. Not limited to bio-related systems, 452,453 the ways of materials construction by nanoarchitectonics would become nice guides for developments of functional systems in chemistry including synthesis of novel molecules, 454,455 fabrication and functionalization of low-dimensional materials, 456,457 and construction of hybrid materials, 458 and others.…”

Section: Resultsmentioning

confidence: 99%

Chemistry Can Make Strict and Fuzzy Controls for Bio-Systems: DNA Nanoarchitectonics and Cell-Macromolecular Nanoarchitectonics

Komiyama

Yoshimoto

Sisido

et al. 2017

Bulletin of the Chemical Society of Japan

281

131

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In this review, we introduce two kinds of bio-related nanoarchitectonics, DNA nanoarchitectonics and cellmacromolecular nanoarchitectonics, both of which are basically controlled by chemical strategies. The former DNA-based approach would represent the precise nature of the nanoarchitectonics based on the strict or "digital" molecular recognition between nucleic bases. This part includes functionalization of single DNAs by chemical means, modification of the main-chain or side-chain bases to achieve stronger DNA binding, DNA aptamers and DNAzymes. It also includes programmable assemblies of DNAs (DNA Origami) and their applications for delivery of drugs to target sites in vivo, sensing in vivo, and selective labeling of biomaterials in cells and in animals. In contrast to the digital molecular recognition between nucleic bases, cell membrane assemblies and their interaction with macromolecules are achieved through rather generic and "analog" interactions such as hydrophobic effects and electrostatic forces. This cell-macromolecular nanoarchitectonics is discussed in the latter part of this review. This part includes bottom-up and top-down approaches for constructing highly organized cell-architectures with macromolecules, for regulating cell adhesion pattern and their functions in twodimension, for generating three-dimensional cell architectures on micro-patterned surfaces, and for building synthetic/natural macromolecular modified hybrid biointerfaces.

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Synthesis and Reactivity of Functionalized Silicon(II) Compounds: Iminosilylene, Phosphinosilylene, Hydrosilylene, and Related Compounds

Cited by 26 publications

References 155 publications

NHCs in Main Group Chemistry

NHCs in Main Group Chemistry

Hafnocene-based Bicyclo[2.1.1]hexene Germylenes – Formation, Reactivity, and Structural Flexibility

Chemistry Can Make Strict and Fuzzy Controls for Bio-Systems: DNA Nanoarchitectonics and Cell-Macromolecular Nanoarchitectonics

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