Synthesis of a Stable Disilyne Bisphosphine Adduct and Its Non‐Metal‐Mediated CO<sub>2</sub> Reduction to CO

Gau, David; Rodrı́guez, Ricardo; Kato, Tsuyoshi; Saffon‐Merceron, Nathalie; Cózar, Abel de; Cossío, Fernando P.; Baceiredo, Antoine

doi:10.1002/anie.201006265

Cited by 125 publications

(69 citation statements)

References 52 publications

(33 reference statements)

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“…In this case, CO 2 activation is initiated by attack of the lone pair of electrons on the silicon atom to the electropositive carbon atom to form Lewis adduct IT1_4 (–11.7 kcal mol –1 ). The successive three‐membered Si–C–O ring transition state (see TS1_4 , –11.1 kcal mol –1 ) represents a very small barrier for the formation of the NHC‐stabilized zwitterionic silaaldeyde analogue (see IT2_4 , –18.4 kcal mol –1 ) and concomitant release of CO.[15b],…”

Section: Resultsmentioning

confidence: 99%

“…For instance, the group of Baceiredo and Kato reported two reactions of silylenes with CO 2 that led to oxygen abstraction (see compound H , Figure ) or bonding as a carbonic acid derivative (see compound I , Figure ) . In addition, an interesting reaction of an dialkylsilylene with CO 2 and H 2 O was reported by Li, Kira, and co‐workers . Very recently, our group reported the reaction of an NHC‐stabilized cationic silicon(II) compound (i.e., silyliumylidene ion) with CO 2 to give rise to acylium ion analogue J (Figure ) …”

Section: Introductionmentioning

confidence: 89%

“…Whereas there has been vast research on the activation of CO 2 , the reactivity of CO 2 with silylenes is far less explored than that of ketones and aldehydes. For instance, the group of Baceiredo and Kato reported two reactions of silylenes with CO 2 that led to oxygen abstraction (see compound H , Figure ) or bonding as a carbonic acid derivative (see compound I , Figure ) . In addition, an interesting reaction of an dialkylsilylene with CO 2 and H 2 O was reported by Li, Kira, and co‐workers .…”

Section: Introductionmentioning

confidence: 96%

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Reactivity of an N‐Heterocyclic Carbene Stabilized Hydrosilylene towards a Ketone and CO2: Experimental and Theoretical Study

Eisenhut

Breit

Szilvási³

et al. 2016

Eur J Inorg Chem

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The reaction of N‐heterocyclic carbene (NHC)‐stabilized hydrosilylene 1, tBu3SiSi(H)←NHC, with one and two equivalents of benzophenone gave rise to bicyclic compounds 2 and 3, tBu3Si(R)[Si‐CH2‐N(CMeCMeNMe)‐CPh2‐O] (R = H, OCHPh2). The NHC plays a crucial role in this reactivity, as it is directly involved in C–C bond formation and supplies the C–H‐activated methyl group. In the formation of 3, the terminal Si–H bond of the hydrosilylene is involved in transition‐metal‐free hydrosilylation. All steps in these mechanisms are based on NHC‐stabilized zwitterionic transition states and intermediates and were investigated by utilizing DFT calculations. In addition, the CO2 activation of 1 to yield cis/trans‐cyclotrisiloxane 4, [(tBu3Si)(H)Si‐O]3, stereoselectively and its mechanistic study are reported.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 89%

Section: Introductionmentioning

confidence: 96%

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Reactivity of an N‐Heterocyclic Carbene Stabilized Hydrosilylene towards a Ketone and CO2: Experimental and Theoretical Study

Eisenhut

Breit

Szilvási³

et al. 2016

Eur J Inorg Chem

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“…[17,18] TheC = Ob ond (1.217(4) )i sl onger than in 2 and 3,a nd the CÀOs ingle bonds were found to be 1.32 (average) indicating adegree of delocalization across the CO 3 unit. Crystallographic analysis revealed that compound 4 consists of asix-membered ring containing abridging carbonate group and oxygen between the two aluminum centers,r eminiscent of the cyclic silicon structures reported.…”

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confidence: 95%

“…Donor-stabilized bis(silylene) [17] and ad isilicon(0) species [18] showed that CO 2 binding and subsequent CÀO cleavage resulted in carbonate formation, whereas reaction of adigermyne with CO 2 , [19] which is also thought to contain some multiple-bond character,resulted in oxygen abstraction and concomitant formation of CO.E xamples of C À O cleavage has also been observed in f-element chemistry,i n particular for U III complexes,where CO 2 cleavage to CO and Oh as been noted to occur at room temperature. [20,21] Whilst the reactivity of Group 14 [22] and boron multiple bonds [23] is rather well-established, aluminum multiple-bond chemistry is still in its infancy.…”

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confidence: 99%

CO₂Fixation and Catalytic Reduction by a Neutral Aluminum Double Bond

Weetman¹,

Bag²,

Szilvási

et al. 2019

Angewandte Chemie

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CO 2 fixation and reduction to value-added products is of utmost importance in the battle against rising CO 2 levels in the Earthsa tmosphere.A no rganoaluminum complex containing aformal aluminum double bond (dialumene), and thus an alkene equivalent, was used for the fixation and reduction of CO 2 .The CO 2 fixation complex undergoes further reactivity in either the absence or presence of additional CO 2 ,r esulting in the first dialuminum carbonyl and carbonate complexes, respectively.D ialumene (1)c an also be used in the catalytic reduction of CO 2 ,p roviding selective formation of af ormic acid equivalent via the dialuminum carbonate complex rather than aconventional aluminum-hydride-basedc ycle.N ot only are the CO 2 reduction products of interest for C 1 added value products,b ut the organoaluminum complexes isolated represent as ignificant step forwardi nt he isolation of reactive intermediates proposed in many industrially relevant catalytic processes.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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A Dimer of Silaisonitrile with Two‐Coordinate Silicon Atoms

et al. 2011

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Dedicated to Professor Raymundo Cea-Olivares on the occasion of his 60th birthday Carbenes and silylenes are among the most important reactive intermediates of carbon [1] and silicon. [2,3] These species play key roles in numerous thermal and photochemical reactions and are extremely important in synthetic chemistry. [1][2][3] The first N-heterocyclic carbene (NHC) that is stable at room temperature was isolated by Arduengo et al. in 1991. [4] The silicon analogue of NHC was reported three years later by West and co-workers [5] as an N-heterocyclic silylene (NHSi) and using the same stabilization concept. Since then, a number of stable carbene [6, 7] and silylene [8] compounds have been isolated with various electronic structures and properties. Synthesis and stabilization of the reactive species are not just a simple desire of academic interest to realize highly reactive molecules at normal laboratory conditions; they have also found many useful applications. [7][8][9][10] The extraordinary electronic properties of NHCs as strong s-donor and weak p-acceptor ligands have been shown to bind more strongly with transition metals than classical ligands. [7, 9] The unusual stability of transition-metal complexes supported by NHC as ligands has led to a major breakthrough in the second generation of Grubbs catalysts. [10] The properties of silicon and carbon are rather different from each other although both have the same number of valence electrons. These differences are most pronounced for compounds with low-coordinate silicon and carbon atoms. Among unsaturated compounds, a wide range of carbon compounds are known that are stable, whereas analogous silicon compounds are very limited and quite reactive. The syntheses of stable silicon compounds have been inspired almost exclusively by their relationship with organic congeners. Silicon analogues of alkenes, [11] alkynes, [12] allenes, [13] and other unsaturated organic compounds with a C=X (X = O or S) functional group [14,15] have been prepared. The molec-ular and electronic structures of unsaturated compounds of silicon are very different from those of the corresponding carbon compounds in which s/p hybridization models are valid. [16,17] To understand the physical and chemical properties of unsaturated silicon compounds, additional experimental investigations are required. Further progress and understanding of the field depend on the availability of appropriate stable silicon compounds.Organic nitriles and isonitriles are very stable, but their silicon analogues are only detected as transient species in a low-temperature argon matrix. [18][19][20] The first transient silaisonitrile, HN = Si, was described in 1966 by Ogilvie and Cradock; [19] this species was generated by photolysis of H 3 SiN 3 in an argon matrix at 4 K. The formation of silaisonitrile [20] was shown by PE and IR spectroscopic studies in an argon matrix. Quantum chemical calculations have shown that silaisonitriles are more stable than silanitriles. [21] This result is in contrast to the ca...

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Synthesis of a Stable Disilyne Bisphosphine Adduct and Its Non‐Metal‐Mediated CO₂ Reduction to CO

Cited by 125 publications

References 52 publications

Reactivity of an N‐Heterocyclic Carbene Stabilized Hydrosilylene towards a Ketone and CO2: Experimental and Theoretical Study

Reactivity of an N‐Heterocyclic Carbene Stabilized Hydrosilylene towards a Ketone and CO2: Experimental and Theoretical Study

CO₂Fixation and Catalytic Reduction by a Neutral Aluminum Double Bond

A Dimer of Silaisonitrile with Two‐Coordinate Silicon Atoms

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Synthesis of a Stable Disilyne Bisphosphine Adduct and Its Non‐Metal‐Mediated CO2 Reduction to CO

Cited by 125 publications

References 52 publications

Reactivity of an N‐Heterocyclic Carbene Stabilized Hydrosilylene towards a Ketone and CO2: Experimental and Theoretical Study

Reactivity of an N‐Heterocyclic Carbene Stabilized Hydrosilylene towards a Ketone and CO2: Experimental and Theoretical Study

CO2Fixation and Catalytic Reduction by a Neutral Aluminum Double Bond

A Dimer of Silaisonitrile with Two‐Coordinate Silicon Atoms

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Product

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Synthesis of a Stable Disilyne Bisphosphine Adduct and Its Non‐Metal‐Mediated CO₂ Reduction to CO

CO₂Fixation and Catalytic Reduction by a Neutral Aluminum Double Bond