Reactions of CS2 and C(S)NPh Adducts of N‐Heterocyclic Carbenes with [Ru3(CO)12]: Remarkable Reactivity of These Betaines Involving One or Two C–S Bond Activation Processes

Cabeza, Javier A.; García‐Álvarez, Pablo; Hernández-Cruz, María G.

doi:10.1002/ejic.201200245

Cited by 13 publications

(4 citation statements)

References 55 publications

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“…Indeed, we and others have already reported the synthesis of a wide variety of transition metal complexes featuring monodentate, [3] chelating bidentate, [4] or bridging bidentate NHC•CS 2 ligands, [3b,4f,g] as well as small bimetallic clusters of manganese [4g] and rhenium. [4f] Copper-based coordination polymers [5] and clusters, [6] or gold nanoparticles [3b] and self-assembled monolayers [7] based on these zwitterions were also described in the literature, while a few reports disclosed the formation of polynuclear iron [8] or ruthenium [9] clusters, in which the dithiocarboxylate unit underwent further chemical transformations.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Azolium‐2‐dithiocarboxylate Zwitterions under Mild, Aerobic Conditions

et al. 2021

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This paper is dedicated to Professor Pierre Dixneuf for his outstanding contributions to organometallic chemistry and homogeneous catalysis, especially with ruthenium-arene complexes.Twelve imidazolium-, imidazolinium-, or benzimidazolium-2dithiocarboxylate zwitterions with aliphatic or aromatic substituents on their nitrogen atoms, including four new unsymmetrical 1-alkyl-3-arylimidazolium derivatives, were obtained in high yields (62-96 %) upon reaction of azolium salts with CS 2 and Cs 2 CO 3 in acetonitrile at room temperature. Compared to the previous strategies devised for the synthesis of NHC•CS 2 betaines, this novel procedure relied on an innocuous, weak base and could be applied under mild aerobic conditions. All the new compounds were fully characterized by various analytical techniques and the molecular structures of two of them were determined by XRD analysis. An associative mechanism involving the concerted reaction of the azolium salts with both CS 2 and CO 3 2À was tentatively proposed to account for the formation of the zwitterionic adducts without the intervention of free carbenes. This would explain the good results obtained with a weak inorganic base that lacks the strength needed to deprotonate the azolium salt substrates.

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Section: Introductionmentioning

confidence: 99%

Synthesis of Azolium‐2‐dithiocarboxylate Zwitterions under Mild, Aerobic Conditions

et al. 2021

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“…Indeed, we and others have already reported the synthesis of diverse metallic complexes featuring monodentate [44,45], chelating bidentate [46][47][48][49][50][51][52][53][54][55], or bridging bidentate NHC•CS 2 ligands [45,51,52]. Small bimetallic clusters [51,52,56], coordination polymers [57], self-assembled monolayers [58], and nanoparticles [45] based on these zwitterions were also prepared, while a few reports disclosed the formation of polynuclear clusters, in which the dithiocarboxylate unit underwent further chemical transformations [59][60][61].…”

Section: Introductionmentioning

confidence: 99%

Aldiminium and 1,2,3-triazolium dithiocarboxylate zwitterions derived from cyclic (alkyl)(amino) and mesoionic carbenes

Touj,

Mazars,

Zaragoza

et al. 2023

Beilstein J. Org. Chem.

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The synthesis of zwitterionic dithiocarboxylate adducts was achieved by deprotonating various aldiminium or 1,2,3-triazolium salts with a strong base, followed by the nucleophilic addition of the in situ-generated cyclic (alkyl)(amino) or mesoionic carbenes (CAACs or MICs) onto carbon disulfide. Nine novel compounds were isolated and fully characterized by 1H and 13C NMR, FTIR, and HRMS techniques. Moreover, the molecular structures of two CAAC·CS2 and two MIC·CS2 betaines were determined by X-ray diffraction analysis. The analytical data recorded for all these adducts were compared with those reported previously for related NHC·CS2 betaines derived from imidazolinium or (benz)imidazolium salts. Due to the absence of electronic communication between the CS2 unit and the orthogonal heterocycle, all the CAAC·CS2, MIC·CS2, and NHC·CS2 zwitterions displayed similar electronic properties and featured the same bite angle. Yet, their steric properties are liable to ample modifications by varying the exact nature of their cationic heterocycle and its substituents.

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“…More recently, we disclosed the synthesis of superbulky imidazolium-2-dithiocarboxylate ligands and their complexation to rhenium and ruthenium, while other researchers relied on NHC·CS 2 betaines to prepare copper-based coordination polymers and clusters or gold nanoparticles and self-assembled monolayers . A few reports on the formation of dinuclear iron–carbonyl and tetranuclear ruthenium–carbonyl clusters, in which the dithiocarboxylate unit underwent chemical transformations, also appeared in the literature.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Biological Activity of Water-Soluble, Dual Anionic and Cationic Ruthenium–Arene Complexes Bearing Imidazol(in)ium-2-dithiocarboxylate Ligands

et al. 2021

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An efficient synthetic protocol was devised for the preparation of five cationic ruthenium−arene complexes bearing imidazol(in)ium-2-dithiocarboxylate ligands from the [RuCl 2 (pcymene)] 2 dimer and 2 equiv of an NHC•CS 2 zwitterion. The reactions proceeded cleanly and swiftly in dichloromethane at room temperature to afford the expected [RuCl(p-cymene)(S 2 C•NHC)]Cl products in quantitative yields. When the [RuCl 2 (p-cymene)] 2 dimer was reacted with only 1 equiv of a dithiolate betaine under the same experimental conditions, a set of five bimetallic compounds with the generic formulawas obtained in quantitative yields. These novel, dual anionic and cationic ruthenium−arene complexes were fully characterized by various analytical techniques. NMR titrations showed that the chelation of the dithiocarboxylate ligands to afford [RuCl(pcymene)(S 2 C•NHC)] + cations was quantitative and irreversible. Conversely, the formation of the [RuCl 3 (p-cymene)] − anion was limited by an equilibrium, and this species readily dissociated into Cl − anions and the [RuCl 2 (p-cymene)] 2 dimer. The position of the equilibrium was strongly influenced by the nature of the solvent and was rather insensitive to the temperature. Two monometallic and two bimetallic complexes cocrystallized with water, and their molecular structures were solved by X-ray diffraction analysis. Crystallography revealed the existence of strong interactions between the azolium ring protons of the cationic complexes and neighboring donor groups from the anions or the solvent. The various compounds under investigation were highly soluble in water. They were all strongly cytotoxic against K562 cancer cells. Furthermore, with a selectivity index of 32.1, the [RuCl(pcymene)(S 2 C•SIDip)]Cl complex remarkably targeted the erythroleukemic cells vs mouse splenocytes.

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Reactions of CS₂ and C(S)NPh Adducts of N‐Heterocyclic Carbenes with [Ru₃(CO)₁₂]: Remarkable Reactivity of These Betaines Involving One or Two C–S Bond Activation Processes

Cited by 13 publications

References 55 publications

Synthesis of Azolium‐2‐dithiocarboxylate Zwitterions under Mild, Aerobic Conditions

Synthesis of Azolium‐2‐dithiocarboxylate Zwitterions under Mild, Aerobic Conditions

Aldiminium and 1,2,3-triazolium dithiocarboxylate zwitterions derived from cyclic (alkyl)(amino) and mesoionic carbenes

Synthesis, Characterization, and Biological Activity of Water-Soluble, Dual Anionic and Cationic Ruthenium–Arene Complexes Bearing Imidazol(in)ium-2-dithiocarboxylate Ligands

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