Biologically Active N-Heterocyclic Carbene–Metal Complexes

Deblock, Michael C.; Panzner, Matthew J.; Tessier, Claire A.; Cannon, Carolyn L.; Youngs, Wiley J.

doi:10.1039/9781849732161-00119

Cited by 3 publications

(3 citation statements)

References 31 publications

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“…However, the diversity of structures among SNCs has also expanded to include other heteroatoms such as sulfur, oxygen, and phosphorus and indeed no heteroatom at all in the case of carbanionic-stabilized carbene centers and cyclopropenylidenes. − Additionally, many acyclic variants are known. Their coordination chemistry is not limited to transition metals as they also bind to non-transition-metal elements ranging from the s-block elements through the p-block and even the lanthanides. − NHCs have shown remarkable utility not only as privileged ligands for a broad range of transition-metal catalytic systems but also as potent catalytic species on their own − , Moreover, NHCs have found utility in a wide range of medical, luminescent, and other functional materials. − …”

Section: Introductionmentioning

confidence: 99%

Bond Dissociation Energies of Carbene–Carbene and Carbene–Main Group Adducts

et al. 2022

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A range of carbene structures and their adducts with one another and with a selection of small-molecule electrophiles and nucleophiles were examined at the composite correlated molecular orbital theory G3MP2 level to explore ground-state "carbenic" structures, their stabilities, and reactivities. Differences between carbene general classification as a singlet electrophilic carbene or singlet nucleophilic carbene and their given reactivity are discussed. A key quantity is the carbon−carbon bond dissociation energy for carbene dimers or the carbene-adduct dissociation energy for other species. The carbene dimer bond dissociation energies span a wide range from 10 to 170 kcal/mol. The hydrogenation energies and singlet−triplet splitting were found to correlate best with the carbene's self-dimerization energy, whereas other descriptors do not. The proton and fluoride affinities of the carbenes alone prove inadequate for classifying reactivity among classes of carbenes. The self-dimerization bond dissociation energy, hydrogenation energy, and singlet−triplet splitting of various carbenes, despite sometimes large differences in proton affinity and other indicators of reactivity, provide usable metrics to correlate substantial amounts of thermodynamic and kinetic (reactivity) information regarding these structures.

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Section: Introductionmentioning

confidence: 99%

Bond Dissociation Energies of Carbene–Carbene and Carbene–Main Group Adducts

et al. 2022

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“…The use of gold compounds as therapeutic agents, [95][96][97] biologically active NHC metal complexes 98 and some aspects of gold(I) protein interactions 99 were reviewed. Amino pyridine Ag complexes with substituted benzoic acid ligands were synthesised and tested against bacteria 100 and cancer cell lines.…”

Section: Biochemical Studiesmentioning

confidence: 99%

Silver and gold

Meyer

Schuh

Seeger

et al. 2012

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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This article reviews the literature reported during 2011 on gold and silver coordination and organometallic chemistry, focusing on synthetic applications (catalysis, coupling reactions, transmetallation), photochemical properties, biochemical studies as well as compounds with unique structural features. Gold and silver nanomaterials, self-assembled monolayers on Au surfaces as well as other metallic compounds (alloys) of gold and silver are not included.

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“…The chemistry of coinage metal complexes containing N -heterocyclic carbene (NHC) ligands has been expanding rapidly due to the relevance of such compounds in catalysis, materials science, and in particular for pharmaceutical applications [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 ]. 1,2,4-Triazol-5-ylidenes have been neglected in this context.…”

Section: Introductionmentioning

confidence: 99%

Coinage Metal Complexes of the Carbenic Tautomer of a Conjugated Mesomeric Betaine Akin to Nitron

et al. 2017

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This study was motivated by our recent observation that the analytical reagent Nitron (2) is an “instant carbene”, whose reaction with coinage metal salts MX afforded complexes of its carbenic tautomer 1,4-diphenyl-3-phenylamino-1,2,4-triazol-5-ylidene (2′). Our aim was to establish an alkyl homologue of 2 in order to achieve a carbenic tautomer of higher donicity. For this purpose 1-tert-butyl-4-methyl-1,2,4-triazol-4-ium-3-tert-butylaminide (6) was synthesized. Its reactions with MX afforded complexes of the carbenic tautomer 1-tert-butyl-3-tert-butylamino-4-methyl-1,2,4-triazol-5-ylidene (6′). With a stoichiometric ratio of 1:1 complexes of the type [MX(6′)] were obtained. A ratio of 2:1 furnished complexes of the type [MX(6′)2] or [M(6′)2]X. 6′ is a better σ-donor and less electrophilic than 2′ according to NMR spectroscopic data of 6H[BF4] and 6′ = Se, respectively, and IR spectroscopic data of [RhCl(6′)(CO)2] confirm that its net electron donor capacity is superior to that of 2′. A comparison of the complexes of 2′ and 6′ reveals two pronounced structural differences. [CuX(6′)2] (X = Cl, Br) exhibit more acute C–Cu–C bond angles than [CuX(2′)2]. In contrast to [CuCl(2′)], [CuCl(6′)] aggregates through Cu···Cu contacts of ca. 2.87 Å, compatible with cuprophilic interactions. These differences may be explained by the complementary steric requirements of the t-Bu and the Me substituent of 6′.

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Biologically Active N-Heterocyclic Carbene–Metal Complexes

Cited by 3 publications

References 31 publications

Bond Dissociation Energies of Carbene–Carbene and Carbene–Main Group Adducts

Bond Dissociation Energies of Carbene–Carbene and Carbene–Main Group Adducts

Silver and gold

Coinage Metal Complexes of the Carbenic Tautomer of a Conjugated Mesomeric Betaine Akin to Nitron

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