Synthesis, crystal structure and electrochemical study of (μ-κ2C:κ2S-NHC+-CS)[Fe2(CO)6]− generated from the reaction of NHC+-CS2− with Fe3(CO)12

Shi, Yao‐Cheng; Shi, Ying

doi:10.1016/j.ica.2015.04.024

Cited by 12 publications

(7 citation statements)

References 49 publications

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“…1 H NMR spectra of complexes 1-5 looked similar to those recorded previously for the free NHC•CS 2 zwitterions 4 and were therefore of little informative value. Examination of the 13 C NMR data was more instructive, as it confirmed the presence of the dithiocarboxylate unit, which gave rise to a characteristic, highly deshielded singlet at ca. 220-226 ppm.…”

Section: Synthesis Of Mononuclear [Rebr(co) 3 (S 2 C•nhc)] Complexesmentioning

confidence: 99%

“…1 H NMR analysis of complexes 6-8 confirmed the presence of an imidazolium fragment in these compounds. Additional structural information came from 13 C NMR spectroscopy, which showed three weak resonances with relative intensities 1 : 1 : 2 in the 190-210 ppm region. This pattern nicely reflected the presence of 2 axial, 2 interaxial, and 4 equatorial CO groups within the octacarbonyl compounds under scrutiny.…”

Section: Synthesis Of Dinuclear [Re 2 (Co) 8 (S 2 C•nhc)] Complexesmentioning

confidence: 99%

“…When the imidazolinium-based mononuclear complexes 4 and 5 were reacted with a small excess of Na[Re(CO) 5 ] in THF at room temperature, 13 C NMR analysis showed the appearance of a singular peak at ca. 79 ppm, in addition to the resonances expected for μ 2 -κ 1 -S,κ 1 -S′-bridging SIMes•CS 2 or SIDip•CS 2 ligands.…”

Section: Synthesis Of Dinuclear [Re 2 (Co) 6 (S 2 C•nhc)] Clustersmentioning

confidence: 99%

“…4 Moreover, they did not reveal the formation of mixtures containing hexa-and octacarbonyl derivatives when monometallic complexes 4 and 5 were reacted with Na[Re (CO) 5 ] in THF at room temperature. 13 C NMR spectroscopy provided a much better tool to monitor the decarbonylation of the bimetallic complexes. Indeed, the coordination of a dithiocarboxylate unit to a rhenium center via its central carbon atom led to a dramatic shielding of this nucleus, whose chemical shift decreased from ca.…”

Section: And the Esi †)mentioning

confidence: 99%

“…9 Contrastingly, recourse to various gold(I) precursors afforded either monometallic products featuring a κ 1 -S binding mode of the zwitterionic ligand or bimetallic compounds with a μ 2 -κ 1 -S,κ 1 -S′ bridging unit. 10 Other polymetallic entities recently elaborated through the use of imidazolium-2-dithiocarboxylate betaines include gold(0) nanoparticles 10 and self-assembled monolayers, 11 copper(I)-based linear coordination polymers, 12 and iron(0) 13 or ruthenium(0) carbonyl clusters. 14 Rhenium has triggered a lot of interest in organometallic chemistry due to its wide range of oxidation states (from −III to +VII) and the radioactivity of two of its isotopes ( 186 Re and 188 Re) that can be easily produced and are therefore suitable for radiotherapeutic purposes.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, characterization, and gas-phase fragmentation of rhenium–carbonyl complexes bearing imidazol(in)ium-2-dithiocarboxylate ligands

2016

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Five complexes with the generic formula [ReBr(CO)(κ-S,S'-SC·NHC)] were obtained by reacting [ReBr(CO)] with a set of representative imidazol(in)ium-2-dithiocarboxylate zwitterions. These ligands are the adducts of N-heterocyclic carbenes (NHCs) and carbon disulfide. The monometallic Re(i) compounds were further coupled with Na[Re(CO)] to afford bimetallic Re(0) species. Depending on the experimental conditions, either octacarbonyl dimers [Re(CO)(μ-κ-S,κ-S'-SC·NHC)] or hexacarbonyl clusters [Re(CO)(κ-S,S'-κ-S,C,S'-SC·NHC)] were isolated. All the products were fully characterized using various analytical techniques. Single crystal XRD analysis helped establish with certainty the various binding modes exhibited by the NHC·CS ligands. With bite angles ranging from ca. 104 to 130°, these zwitterions displayed a remarkable flexibility, which also permitted significant twists of the thiometallated rings to preserve a staggered arrangement of the carbonyl groups in the bimetallic systems. Monitoring the chemical shift of the CS moiety by C NMR spectroscopy was most useful to detect its change of hapticity upon decarbonylation of the octacarbonyl compounds into hexacarbonyl derivatives. IR spectroscopy was another very convenient tool to identify the type of complex formed in a reaction, based on the pattern of its carbonyl vibration bands. Advanced mass spectrometry techniques showed that all the compounds underwent partial or total decarbonylation in the gas phase with no concomitant fragmentation of the bimetallic assemblies into monometallic ions.

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Section: Synthesis Of Mononuclear [Rebr(co) 3 (S 2 C•nhc)] Complexesmentioning

confidence: 99%

Section: Synthesis Of Dinuclear [Re 2 (Co) 8 (S 2 C•nhc)] Complexesmentioning

confidence: 99%

Section: Synthesis Of Dinuclear [Re 2 (Co) 6 (S 2 C•nhc)] Clustersmentioning

confidence: 99%

Section: And the Esi †)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis, characterization, and gas-phase fragmentation of rhenium–carbonyl complexes bearing imidazol(in)ium-2-dithiocarboxylate ligands

2016

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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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Recent Advances in Small Clusters and Polymetallic Assemblies Based on Transition Metals and Dithiocarboxylate Zwitterions Derived from N-Heterocyclic Carbenes

Beltrán

Delaude

2017

J Clust Sci

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Synthesis, crystal structure and electrochemical study of (μ-κ2C:κ2S-NHC+-CS)[Fe2(CO)6]− generated from the reaction of NHC+-CS2− with Fe3(CO)12

Cited by 12 publications

References 49 publications

Synthesis, characterization, and gas-phase fragmentation of rhenium–carbonyl complexes bearing imidazol(in)ium-2-dithiocarboxylate ligands

Synthesis, characterization, and gas-phase fragmentation of rhenium–carbonyl complexes bearing imidazol(in)ium-2-dithiocarboxylate ligands

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

Recent Advances in Small Clusters and Polymetallic Assemblies Based on Transition Metals and Dithiocarboxylate Zwitterions Derived from N-Heterocyclic Carbenes

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