Non‐innocent Behaviour of Dithiocarboxylate Ligands Based on N‐Heterocyclic Carbenes

Abstract

Not so innocent: Sterically tuneable dithiocarboxylate ligands derived from N‐heterocyclic carbenes act as excellent bidentate chelates for ruthenium(II) σ‐alkenyl complexes. However, the most sterically demanding member of the ligand family causes a fascinating and unexpected rearrangement to occur (see figure; ICy=1,3‐dicylohexylimidazolium, IDip=1,3‐bis(2,6‐diisopropylphenyl)imidazolium).

Synthesis and Application of Ruthenium(II) Alkenyl Complexes with Perylene Fluorophores for the Detection of Toxic Vapours and Gases

“…These solubilizing units, py-PEG3 and HCC-PEG3,w ere fully characterised by 1 H, 13 C{ 1 H} NMR and infrared spectroscopiesa nd mass spectrometry.Both py-PEG3 and HCC-PEG3, were obtained as pale yellow oils after purification by column chromatography in DCM/MeOH mixtures. Characteristic signals were observed, such as the 5.26 ppm singlet attributedt ot he terminal alkyne in the 1 HNMR spectrum (see Supporting Information).…”

“…[10a] Our work hasf ocused on the analogous2 ,1,3-benzothiadiazole (BTD) complexes, including osmium examples, [10b] which use the cheaper BTD heterocycle. Through the lability of the chloride and phosphine ligands (and BTD/BSD, if present), mono-, [11,12] bi- [13,14,15] and tridentate [16] donors can be coordinated to these vinyl compounds. This provides ample demonstration of the reactivity at the metal centre, however,t he installation of the vinyl ligand through facile reaction with terminal alkynes (also internal alkynes under more forcingc onditions) allows the incorporation of furtherf unctionality that can be influenced by the metal centre.…”

Synthesis and characterization of ruthenium complexes with 1-aryl-2-mercaptoimidazole ligands

“…Herein, we report the reactions of vinyl ruthenium complexes with 1-aryl-2-mercaptoimidazole ligands (Scheme 1). [14]. In the initial experiments we investigated the reactions of 1-aryl-2-mercaptoimidazole (HL) with Ru(CH]CHPh)Cl(CO)(PPh 3 ) 2 (1) using a slightly modified procedure reported by Wilton-Ely and coworkers [15].…”

A Sophisticated Approach towards a New Class of Copper(I)–Sulfur Cluster Complexes with Imidazolinium–Dithiocarboxylate Ligands

“…Today, a limited number of metal complexes with gold, palladium, ruthenium, osmium,[24b] rhenium,[24c], manganese, manganese–rhenium, cadmium, and mercury, as well as zinc, are known. Beyond that, investigations of catalytic potentials and other features have been performed with some of the complexes, [22b], , and the free betaines…”