N-heterocyclic carbene supported halosilylenes: New frontiers in an emerging field

The history of silyl cations has all the makings of a drama but with a happy ending. Being considered reactive intermediates impossible to isolate in the condensed phase for decades, their actual characterization in solution and later in solid state did only fuel the discussion about their existence and initially created a lot of controversy. This perception has completely changed today, and silyl cations and their donor-stabilized congeners are now widely accepted compounds with promising use in synthetic chemistry. This review provides a comprehensive summary of the fundamental facts and principles of the chemistry of silyl cations, including reliable ways of their preparation as well as their physical and chemical properties. The striking features of silyl cations are their enormous electrophilicity and as such reactivity as super Lewis acids as well as fluorophilicity. Known applications rely on silyl cations as reactants, stoichiometric reagents, and promoters where the reaction success is based on their steady regeneration over the course of the reaction. Silyl cations can even be discrete catalysts, thereby opening the next chapter of their way into the toolbox of synthetic methodology.

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“…However, the recent advances in this field might turn this method into a more general appoach toward silyl cations in the future. 150,151…”

Section: Synthesis By Addition Of Electrophiles To Silylenesmentioning

confidence: 99%

Silylium Ions: From Elusive Reactive Intermediates to Potent Catalysts

et al. 2021

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“…The ability to control this equilibrium provides a new route to access to the more reactive silylsilylene species. Two‐coordinate acyclic silylenes are highly reactive species as they contain a vacant coordination site and a lone pair, and as such have shown facile bond activations towards small molecules and a variety of substrates [24, 28, 105–107] . It could be envisaged that new catalytic cycles, based on the ability to control this equilibrium, could be achieved in a somewhat similar fashion to that depicted in Scheme 1 B.…”

Section: Group 14 Multiple Bondsmentioning

confidence: 99%

“…Two-coordinate acyclic silylenes are highly reactives pecies as they contain av acant coordination site and al one pair,a nd as such have shown facile bond activations towards small molecules and av ariety of substrates. [24,28,[105][106][107] It could be envisaged that new catalytic cycles, based on the ability to control this equilibrium, could be achieved in as omewhat similar fashion to that depicted in Scheme 1B.W herein the multiple bond (disilene) is off cycle and the "active" species is the low valent main group centre (silylsilylene).…”

Section: Multiple Bondsmentioning

confidence: 99%

Main Group Multiple Bonds for Bond Activations and Catalysis

Weetman

2020

Chemistry A European J

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Since the discovery that the so‐called “double‐bond” rule could be broken, the field of molecular main group multiple bonds has expanded rapidly. With the majority of homodiatomic double and triple bonds realised within the p‐block, along with many heterodiatomic combinations, this Minireview examines the reactivity of these compounds with a particular emphasis on small molecule activation. Furthermore, whilst their ability to act as transition metal mimics has been explored, their catalytic behaviour is somewhat limited. This Minireview aims to highlight the potential of these complexes towards catalytic application and their role as synthons in further functionalisations making them a versatile tool for the modern synthetic chemist.

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“…The formation of such unsaturated organosilicon systems is unlikely at Earth's conditions (0-100 • C temperature regime; abundance of liquid water; O 2 -rich atmosphere). However, recent developments in organosilicon synthetic chemistry show that silanes (silicon analogues of hydrocarbons) can undergo a versatile chemistry under conditions that are very different from Earth's environment (cryogenic conditions; lack of liquid water; no O 2 [223]). We discuss some such exceptional silicon chemistry briefly below.…”

Section: Appendix C Formation Of Unsaturated Organosilicon Compoundsmentioning

confidence: 99%

On the Potential of Silicon as a Building Block for Life

Petkowski

Bains

Seager

2020

Life

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Despite more than one hundred years of work on organosilicon chemistry, the basis for the plausibility of silicon-based life has never been systematically addressed nor objectively reviewed. We provide a comprehensive assessment of the possibility of silicon-based biochemistry, based on a review of what is known and what has been modeled, even including speculative work. We assess whether or not silicon chemistry meets the requirements for chemical diversity and reactivity as compared to carbon. To expand the possibility of plausible silicon biochemistry, we explore silicon’s chemical complexity in diverse solvents found in planetary environments, including water, cryosolvents, and sulfuric acid. In no environment is a life based primarily around silicon chemistry a plausible option. We find that in a water-rich environment silicon’s chemical capacity is highly limited due to ubiquitous silica formation; silicon can likely only be used as a rare and specialized heteroatom. Cryosolvents (e.g., liquid N2) provide extremely low solubility of all molecules, including organosilicons. Sulfuric acid, surprisingly, appears to be able to support a much larger diversity of organosilicon chemistry than water.

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N-heterocyclic carbene supported halosilylenes: New frontiers in an emerging field

Cited by 16 publications

References 107 publications

Silylium Ions: From Elusive Reactive Intermediates to Potent Catalysts

Silylium Ions: From Elusive Reactive Intermediates to Potent Catalysts

Main Group Multiple Bonds for Bond Activations and Catalysis

On the Potential of Silicon as a Building Block for Life

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