Destruction of chemical warfare agent simulants by air and moisture stable metal NHC complexes

Weetman, Catherine; Notman, Stuart; Arnold, Polly L.

doi:10.1039/c7dt04805j

Cited by 23 publications

(19 citation statements)

References 40 publications

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“…Research areas where metal mediated organic molecule transformations were conducted using bidentate NHC ligands to a lesser degree include reduction of carbonyl compounds using hydrosilylation process [ 209 , 214 , 215 , 216 , 217 , 218 , 219 ], isomerization of allylic alcohols [ 220 ], cross metathesis [ 221 ], arene borylation [ 222 , 223 ], amination [ 224 ], reduction of sulfoxides [ 225 ], alcohol oxidation [ 132 , 226 , 227 ], CO 2 reduction [ 228 , 229 , 230 , 231 ], norbornene polymerization [ 232 , 233 , 234 ], alkylation of amines [ 235 ], C-H borylation [ 236 ], CO 2 activation [ 237 ], hydroamination [ 238 ], functionalization of propane [ 239 , 240 ], ylide cycloaddition [ 74 ], three component coupling [ 241 ], hydroxylation of benzene [ 242 ], hydroaminoethlyation [ 243 ], water oxidation [ 244 ], amine alkylation [ 245 ], homopolymerization of ethylene [ 246 ], destruction of chemical warfare [ 247 ], Friedel-Crafts alkylation [ 248 ], C–H arylation [ 249 ], C–H oxidation [ 250 ], SABRE catalyst [ 251 ], and alcohol amidation reactions [ 211 ]. S...…”

Section: Synthesis and Applications Of Bidentate Ligands Bearing N-heterocyclic Carbenesmentioning

confidence: 99%

Recent Advances in Catalysis Involving Bidentate N-Heterocyclic Carbene Ligands

2021

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Since the discovery of persistent carbenes by the isolation of 1,3-di-l-adamantylimidazol-2-ylidene by Arduengo and coworkers, we witnessed a fast growth in the design and applications of this class of ligands and their metal complexes. Modular synthesis and ease of electronic and steric adjustability made this class of sigma donors highly popular among chemists. While the nature of the metal-carbon bond in transition metal complexes bearing N-heterocyclic carbenes (NHCs) is predominantly considered to be neutral sigma or dative bonds, the strength of the bond is highly dependent on the energy match between the highest occupied molecular orbital (HOMO) of the NHC ligand and that of the metal ion. Because of their versatility, the coordination chemistry of NHC ligands with was explored with almost all transition metal ions. Other than the transition metals, NHCs are also capable of establishing a chemical bond with the main group elements. The advances in the catalytic applications of the NHC ligands linked with a second tether are discussed. For clarity, more frequently targeted catalytic reactions are considered first. Carbon–carbon coupling reactions, transfer hydrogenation of alkenes and carbonyl compounds, ketone hydrosilylation, and chiral catalysis are among highly popular reactions. Areas where the efficacy of the NHC based catalytic systems were explored to a lesser extent include CO2 reduction, C-H borylation, alkyl amination, and hydroamination reactions. Furthermore, the synthesis and applications of transition metal complexes are covered.

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Section: Synthesis and Applications Of Bidentate Ligands Bearing N-heterocyclic Carbenesmentioning

confidence: 99%

Recent Advances in Catalysis Involving Bidentate N-Heterocyclic Carbene Ligands

2021

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“…Recently, Arnold and co-workers reported that NHC-V(V) adducts 79, 80 and (ICy)VOCl3 were efficient stoichiometric reagents for the destruction of chemical warfare agent simulants (H agent and V agents) through cooperation of the V(V) metal center and the NHC ligand. 68 Thanks to NHC stabilization, Tavčar and coll. structurally characterized the first example of a [(L)VOF3] adduct (79b, Scheme 26).…”

Section: Scmentioning

confidence: 99%

Recent progress on NHC-stabilized early transition metal (group 3–7) complexes: Synthesis and applications

Romain

Bellemin‐Laponnaz

Dagorne

2020

Coordination Chemistry Reviews

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HAL is a multi-disciplinary open access archive for the deposit and dissemination of scientific research documents, whether they are published or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers. L'archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d'enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.

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“… 103 − 107 Beyond this, only a few other applications of vanadium-NHC complexes have been examined, including small molecule activation 108 , 109 and the neutralization of chemical warfare agents. 110 Still, most vanadium NHC complexes refer to diamagnetic vanadium(V) complexes, while low-valent vanadium complexes have been rarely investigated. 101 , 106 , 111 − 114 …”

Section: Introductionmentioning

confidence: 99%

Mesoionic Carbenes in Low- to High-Valent Vanadium Chemistry

et al. 2021

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We report the synthesis of vanadium(V) oxo complex 1 with a pincer-type dianionic mesoionic carbene (MIC) ligand L 1 and the general formula [VOCl(L 1 )]. A comparison of the structural (SC-XRD), electronic (UV–vis), and electrochemical (cyclic voltammetry) properties of 1 with the benzimidazolinylidene congener 2 (general formula [VOCl(L 2 )]) shows that the MIC is a stronger donor also for early transition metals with low d-electron population. Since electrochemical studies revealed both complexes to be reversibly reduced, the stronger donor character of MICs was not only demonstrated for the vanadium(V) but also for the vanadium(IV) oxidation state by isolating the reduced vanadium(IV) complexes [Co(Cp*) 2 ][1] and [Co(Cp*) 2 ][2] ([Co(Cp*) 2 ] = decamethylcobaltocenium). The electronic structures of the compounds were investigated by computational methods. Complex 1 was found to be a moderate precursor for salt metathesis reactions, showing selective reactivity toward phenolates or secondary amides, but not toward primary amides and phosphides, thiophenols, or aryls/alkyls donors. Deoxygenation with electron-rich phosphines failed to give the desired vanadium(III) complex. However, treatment of the deprotonated ligand precursor with vanadium(III) trichloride resulted in the clean formation of the corresponding MIC vanadium(III) complex 6 , which undergoes a clean two-electron oxidation with organic azides yielding the corresponding imido complexes. The reaction with TMS-N 3 did not afford a nitrido complex, but instead the imido complex 10 . This study reveals that, contrary to popular belief, MICs are capable of supporting early transition-metal complexes in a variety of oxidation states, thus making them promising candidates for the activation of small molecules and redox catalysis.

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Destruction of chemical warfare agent simulants by air and moisture stable metal NHC complexes

Cited by 23 publications

References 40 publications

Recent Advances in Catalysis Involving Bidentate N-Heterocyclic Carbene Ligands

Recent Advances in Catalysis Involving Bidentate N-Heterocyclic Carbene Ligands

Recent progress on NHC-stabilized early transition metal (group 3–7) complexes: Synthesis and applications

Mesoionic Carbenes in Low- to High-Valent Vanadium Chemistry

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