0000000000186373

AUTHOR

M. ÁNgeles Fuentes

Catalytic Functionalization of Methane and Light Alkanes in Supercritical Carbon Dioxide

International audience; The development of catalytic methods for the effective functionalization of methane yet remains a challenge. The best system known to date is the so-called Catalytica Process based on the use of platinum catalysts to convert methane into methyl bisulfate with a TOF rate of 10−3 s. In this contribution, we report a series of silver complexes containing perfluorinated tris(indazolyl)borate ligands that catalyze the functionalization of methane into ethyl propionate upon reaction with ethyl diazoacetate (EDA) by using supercritical carbon dioxide (scCO2) as the reaction medium. The employment of this reaction medium has also allowed the functionalization of ethane, prop…

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Cooperative N–H bond activation by amido-Ge(ii) cations

N-heterocyclic carbene (NHC) and tertiary phosphine-stabilized germylium-ylidene cations, [R(L)Ge:]+, featuring tethered amido substituents at R have been synthesized via halide abstraction. Characterization in the solid state by X-ray crystallography shows these systems to be monomeric, featuring a two-coordinate C,N- or P,N-ligated germanium atom. The presence of the strongly Lewis acidic cationic germanium centre and proximal amide function allows for facile cleavage of N-H bonds in 1,2-fashion: the products resulting from reactions with carbazole feature a tethered secondary amine donor bound to a three-coordinate carbazolyl-GeII centre. In each case, addition of the components of the N…

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Reversible O-H bond activation by an intramolecular frustrated Lewis pair

The interactions of the O–H bonds in alcohols, water and phenol with dimethylxanthene-derived frustrated Lewis pairs (FLPs) have been probed. Within the constraints of this backbone framework, the preference for adduct formation or O–H bond cleavage to give the corresponding zwitterion is largely determined by pKa considerations. In the case of the PPh2/B(C6F5)2 system and p-tBuC6H4OH, an equilibrium is established between the two isomeric forms which allows the thermodynamic parameters associated with zwitterion formation via O–H bond cleavage to be probed. peerReviewed

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Probing the non-innocent nature of an amino-functionalised β-diketiminate ligand in silylene/iminosilane systems

Electron-rich β-diketiminate ligands{,} featuring amino groups at the backbone β positions (“N-nacnac” ligands) have been employed in the synthesis of a range of silylene (SiII) complexes of the type (N-nacnac)SiX (where X = H{,} Cl{,} N(SiMe3)2{,} P(SiMe3)2 and Si(SiMe3)3). A combination of experimental and quantum chemical approaches reveals (i) that in all cases rearrangement to give an aza-butadienyl SiIV imide featuring a contracted five-membered heterocycle is thermodynamically favourable (and experimentally viable); (ii) that the kinetic lability of systems of the type (N-nacnac)SiX varies markedly as a function of X{,} such that compounds of this type can be isolated under ambient c…

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Probing the non-innocent nature of an amino-functionalised β-diketiminate ligand in silylene/iminosilane systems.

Electron-rich β-diketiminate ligands, featuring amino groups at the backbone β positions (“N-nacnac” ligands) have been employed in the synthesis of a range of silylene (SiII) complexes of the type (N-nacnac)SiX (where X = H, Cl, N(SiMe3)2, P(SiMe3)2 and Si(SiMe3)3). A combination of experimental and quantum chemical approaches reveals (i) that in all cases rearrangement to give an aza-butadienyl SiIV imide featuring a contracted five-membered heterocycle is thermodynamically favourable (and experimentally viable); (ii) that the kinetic lability of systems of the type (N-nacnac)SiX varies markedly as a function of X, such that compounds of this type can be isolated under ambient conditions …

research product

Reversible O–H bond activation by an intramolecular frustrated Lewis pair

The interactions of the O-H bonds in alcohols, water and phenol with dimethylxanthene-derived frustrated Lewis pairs (FLPs) have been probed. Within the constraints of this backbone framework, the preference for adduct formation or O-H bond cleavage to give the corresponding zwitterion is largely determined by pKa considerations. In the case of the PPh2/B(C6F5)2 system and p-tBuC6H4OH, an equilibrium is established between the two isomeric forms which allows the thermodynamic parameters associated with zwitterion formation via O-H bond cleavage to be probed.

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Approaching a “naked” boryl anion: amide metathesis as a route to calcium, strontium, and potassium boryl complexes

Abstract Amide metathesis has been used to generate the first structurally characterized boryl complexes of calcium and strontium, {(Me3Si)2N}M{B(NDippCH)2}(thf)n (M=Ca, n=2; M=Sr, n=3), through the reactions of the corresponding bis(amides), M{N(SiMe3)2}2(thf)2, with (thf)2Li‐ {B(NDippCH)2}. Most notably, this approach can also be applied to the analogous potassium amide K{N(SiMe3)2}, leading to the formation of the solvent‐free borylpotassium dimer [K{B(NDippCH)2}]2, which is stable in the solid state at room temperature for extended periods (48 h). A dimeric structure has been determined crystallographically in which the K+ cations interact weakly with both the ipso‐carbons of the flanki…

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CCDC 1995924: Experimental Crystal Structure Determination

Related Article: Dinh Cao Huan Do, Petra Vasko, M. Ángeles Fuentes, Jamie Hicks, Simon Aldridge|2020|Dalton Trans.|49|8701|doi:10.1039/D0DT01447H

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CCDC 1952095: Experimental Crystal Structure Determination

Related Article: Xueer Zhou, Petra Vasko, Jamie Hicks, M. Ángeles Fuentes, Andreas Heilmann, Eugene L. Kolychev, Simon Aldridge|2020|Dalton Trans.|49|9495|doi:10.1039/D0DT01960G

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CCDC 1872784: Experimental Crystal Structure Determination

Related Article: Petra Vasko, M. Ángeles Fuentes, Jamie Hicks, Simon Aldridge|2019|Dalton Trans.|48|2896|doi:10.1039/C9DT00228F

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CCDC 1995922: Experimental Crystal Structure Determination

Related Article: Dinh Cao Huan Do, Petra Vasko, M. Ángeles Fuentes, Jamie Hicks, Simon Aldridge|2020|Dalton Trans.|49|8701|doi:10.1039/D0DT01447H

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CCDC 1995923: Experimental Crystal Structure Determination

Related Article: Dinh Cao Huan Do, Petra Vasko, M. Ángeles Fuentes, Jamie Hicks, Simon Aldridge|2020|Dalton Trans.|49|8701|doi:10.1039/D0DT01447H

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CCDC 1872783: Experimental Crystal Structure Determination

Related Article: Petra Vasko, M. Ángeles Fuentes, Jamie Hicks, Simon Aldridge|2019|Dalton Trans.|48|2896|doi:10.1039/C9DT00228F

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CCDC 2005219: Experimental Crystal Structure Determination

Related Article: Xueer Zhou, Petra Vasko, Jamie Hicks, M. Ángeles Fuentes, Andreas Heilmann, Eugene L. Kolychev, Simon Aldridge|2020|Dalton Trans.|49|9495|doi:10.1039/D0DT01960G

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CCDC 1952092: Experimental Crystal Structure Determination

Related Article: Xueer Zhou, Petra Vasko, Jamie Hicks, M. Ángeles Fuentes, Andreas Heilmann, Eugene L. Kolychev, Simon Aldridge|2020|Dalton Trans.|49|9495|doi:10.1039/D0DT01960G

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CCDC 1952094: Experimental Crystal Structure Determination

Related Article: Xueer Zhou, Petra Vasko, Jamie Hicks, M. Ángeles Fuentes, Andreas Heilmann, Eugene L. Kolychev, Simon Aldridge|2020|Dalton Trans.|49|9495|doi:10.1039/D0DT01960G

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CCDC 1872782: Experimental Crystal Structure Determination

Related Article: Petra Vasko, M. Ángeles Fuentes, Jamie Hicks, Simon Aldridge|2019|Dalton Trans.|48|2896|doi:10.1039/C9DT00228F

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CCDC 2021078: Experimental Crystal Structure Determination

Related Article: Andrey V. Protchenko, Petra Vasko, M. Ángeles Fuentes, Jamie Hicks, Dragoslav Vidovic, Simon Aldridge|2021|Angew.Chem.,Int.Ed.|60|2064|doi:10.1002/anie.202011839

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CCDC 1872780: Experimental Crystal Structure Determination

Related Article: Petra Vasko, M. Ángeles Fuentes, Jamie Hicks, Simon Aldridge|2019|Dalton Trans.|48|2896|doi:10.1039/C9DT00228F

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CCDC 2005217: Experimental Crystal Structure Determination

Related Article: Xueer Zhou, Petra Vasko, Jamie Hicks, M. Ángeles Fuentes, Andreas Heilmann, Eugene L. Kolychev, Simon Aldridge|2020|Dalton Trans.|49|9495|doi:10.1039/D0DT01960G

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CCDC 2021077: Experimental Crystal Structure Determination

Related Article: Andrey V. Protchenko, Petra Vasko, M. Ángeles Fuentes, Jamie Hicks, Dragoslav Vidovic, Simon Aldridge|2021|Angew.Chem.,Int.Ed.|60|2064|doi:10.1002/anie.202011839

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CCDC 1952093: Experimental Crystal Structure Determination

Related Article: Xueer Zhou, Petra Vasko, Jamie Hicks, M. Ángeles Fuentes, Andreas Heilmann, Eugene L. Kolychev, Simon Aldridge|2020|Dalton Trans.|49|9495|doi:10.1039/D0DT01960G

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CCDC 1952097: Experimental Crystal Structure Determination

Related Article: Xueer Zhou, Petra Vasko, Jamie Hicks, M. Ángeles Fuentes, Andreas Heilmann, Eugene L. Kolychev, Simon Aldridge|2020|Dalton Trans.|49|9495|doi:10.1039/D0DT01960G

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CCDC 2021075: Experimental Crystal Structure Determination

Related Article: Andrey V. Protchenko, Petra Vasko, M. Ángeles Fuentes, Jamie Hicks, Dragoslav Vidovic, Simon Aldridge|2021|Angew.Chem.,Int.Ed.|60|2064|doi:10.1002/anie.202011839

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CCDC 2021076: Experimental Crystal Structure Determination

Related Article: Andrey V. Protchenko, Petra Vasko, M. Ángeles Fuentes, Jamie Hicks, Dragoslav Vidovic, Simon Aldridge|2021|Angew.Chem.,Int.Ed.|60|2064|doi:10.1002/anie.202011839

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CCDC 1995925: Experimental Crystal Structure Determination

Related Article: Dinh Cao Huan Do, Petra Vasko, M. Ángeles Fuentes, Jamie Hicks, Simon Aldridge|2020|Dalton Trans.|49|8701|doi:10.1039/D0DT01447H

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CCDC 1872781: Experimental Crystal Structure Determination

Related Article: Petra Vasko, M. Ángeles Fuentes, Jamie Hicks, Simon Aldridge|2019|Dalton Trans.|48|2896|doi:10.1039/C9DT00228F

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CCDC 1952091: Experimental Crystal Structure Determination

Related Article: Xueer Zhou, Petra Vasko, Jamie Hicks, M. Ángeles Fuentes, Andreas Heilmann, Eugene L. Kolychev, Simon Aldridge|2020|Dalton Trans.|49|9495|doi:10.1039/D0DT01960G

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CCDC 2005218: Experimental Crystal Structure Determination

Related Article: Xueer Zhou, Petra Vasko, Jamie Hicks, M. Ángeles Fuentes, Andreas Heilmann, Eugene L. Kolychev, Simon Aldridge|2020|Dalton Trans.|49|9495|doi:10.1039/D0DT01960G

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