Bis-Sulfonyl O,C,O-Chelated Metallylenes (Ge, Sn) as Adjustable Ligands for Iron and Tungsten Complexes.

The synthesis and characterization of an E2 CE2 bis-sulfonyl aryl pincer ligand and its efficiency for the stabilization of compounds containing low-valent Group 14 elements (Ge and Sn) are reported. Complexation reaction of these metallylenes with iron or tungsten complexes resulted in the modulation of the oxygen atoms of the sulfonyl groups implicated in the stabilization of the Group 14 elements, demonstrating the original adjustable character of the bis-sulfonyl O2 S-C-SO2 aryl pincer.

Tunable and functional deep eutectic solvents for lignocellulose valorization.

Stabilization of reactive intermediates is an enabling concept in biomass fractionation and depolymerization. Deep eutectic solvents (DES) are intriguing green reaction media for biomass processing; however undesired lignin condensation is a typical drawback for most acid-based DES fractionation processes. Here we describe ternary DES systems composed of choline chloride and oxalic acid, additionally incorporating ethylene glycol (or other diols) that provide the desired 'stabilization' function for efficient lignocellulose fractionation, preserving the quality of all lignocellulose constituents. The obtained ethylene-glycol protected lignin displays high ß-O-4 content (up to 53 per 100 aromatic units) and can be readily depolymerized to distinct monophenolic products. The cellulose residues, free from condensed lignin particles, deliver up to 95.9 ± 2.12% glucose yield upon enzymatic digestion. The DES can be recovered with high yield and purity and re-used with good efficiency. Notably, we have shown that the reactivity of the ß-O-4 linkage in model compounds can be steered towards either cleavage or stabilization, depending on DES composition, demonstrating the advantage of the modular DES composition.

A non-symmetric sulfur-based O,C,O-chelating pincer ligand leading to chiral germylene and stannylene.

New chiral heteroleptic germanium(ii) and tin(ii) metallylenes were obtained using 1-(para-tolylsulfinyl)-3-tosyl-5-tert-butyl-benzene as a non-symmetric O,C,O-chelating pincer ligand. Crystallographic analysis and DFT calculations indicate that the non-symmetric sulfinyl-sulfonyl pincer ligand acts as an O,C,O-coordinating pincer-type-ligand with predominant sulfinyl intramolecular S[double bond, length as m-dash]O coordination to germanium(ii) and tin(ii) centers.