Azolium-2-dithiocarboxylates as redox active ligands in nickel chemistry DOI Creative Commons
Martin S. Luff,

Tin M. Filipovic,

Celine S. Corsei

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

The coordination chemistry of carbene-CS2 adducts selected NHCs and cAACs their redox active nature in nickel complexes is reported. These azolium-2-dithiocarboxylate ligands can be considered as 1,1-isomeric dithiolene analogues bearing a 2π electron reservoir. Depending on the co-ligands attached to nickel, square planar mono- or bis-(carbene-CS2) types [Ni(IiPr)2(carbene-CS2)] (2a-g) (carbene = cAACMe, IDipp, IMes, BIMe, BIiPr, IiPr, IiPrMe) [Ni(carbene-CS2)2] (3a-c) IMes) are accessible by alkene substitution using [Ni(IiPr)2(ƞ2-C2H4)] [Ni(COD)2] starting material (cAACMe 1-(2,6-di-iso-propylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene, IR 1,3-diorganylimidazolin-2-ylidene, IRMe 1,3-diorganyl-4,5-dimethylimidazolin-2-ylidene, BIR 1,3-diorganylbenzimidazolin-2-ylidene). In 2a-g 3a-c, all coordinated κ2-S,S' fashion nickel(ii) ligated either formally one reduced two states. 3a-c reveal intense NIR absorptions, which shift upon metallic reduction nickelate salts type [Cat]+[Ni(carbene-CS2)2]˙- (4a-bcat). these nickelates, an additional shared across ligand-centered SOMO π-symmetry delocalized over both results moieties with formal -1.5 charge per ligand, further demonstrating flexible ligands.

Language: Английский

Isolation and Reactivity of Carbene-Stabilized Carbon Disulfide Radical Anions DOI
Michael J. Stopper, D. Akachukwu, Haleigh R. Machost

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 13, 2025

The reaction of CAAC-CS2 betaine (1; CAAC = cyclic(alkyl)(amino)carbene) and alkali metal reductants under ambient conditions yields carbene-stabilized carbon disulfide radical anions as crystalline salts. radicals 3–5 form multinuclear clusters featuring diverse sulfide interactions, which promote unusual reductive coupling cyclization adjacent CS2 units to C2S3 heterocycles (6). addition crown ethers sequesters the cations facilitates cleavage yield stable [CAAC-CS2]·– monomers (7 8). Calculated natural atomic spin populations suggest that densities in clustered monomeric species are comparable evenly distributed between subunits. Subsequent reductions afford [CAAC-CS2]2– dianions (9–12), can be reoxidized by comproportionation reactions with 1. are, turn, oxidized 1 through salt elimination transition metals. Cyclic voltammograms feature reversible 1/1·–/12– couples a small separation events (ΔΔG 11.1 kcal mol–1). All isolated compounds were characterized combination electron paramagnetic resonance spectroscopy, heteronuclear NMR infrared single-crystal X-ray diffraction. Insights into their electronic structure supported density functional theory calculations.

Language: Английский

Citations

1
Azolium-2-dithiocarboxylates as redox active ligands in nickel chemistry DOI Creative Commons
Martin S. Luff,

Tin M. Filipovic,

Celine S. Corsei

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

The coordination chemistry of carbene-CS2 adducts selected NHCs and cAACs their redox active nature in nickel complexes is reported. These azolium-2-dithiocarboxylate ligands can be considered as 1,1-isomeric dithiolene analogues bearing a 2π electron reservoir. Depending on the co-ligands attached to nickel, square planar mono- or bis-(carbene-CS2) types [Ni(IiPr)2(carbene-CS2)] (2a-g) (carbene = cAACMe, IDipp, IMes, BIMe, BIiPr, IiPr, IiPrMe) [Ni(carbene-CS2)2] (3a-c) IMes) are accessible by alkene substitution using [Ni(IiPr)2(ƞ2-C2H4)] [Ni(COD)2] starting material (cAACMe 1-(2,6-di-iso-propylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene, IR 1,3-diorganylimidazolin-2-ylidene, IRMe 1,3-diorganyl-4,5-dimethylimidazolin-2-ylidene, BIR 1,3-diorganylbenzimidazolin-2-ylidene). In 2a-g 3a-c, all coordinated κ2-S,S' fashion nickel(ii) ligated either formally one reduced two states. 3a-c reveal intense NIR absorptions, which shift upon metallic reduction nickelate salts type [Cat]+[Ni(carbene-CS2)2]˙- (4a-bcat). these nickelates, an additional shared across ligand-centered SOMO π-symmetry delocalized over both results moieties with formal -1.5 charge per ligand, further demonstrating flexible ligands.

Language: Английский

Citations

0