Investigating the formation of metal nitride complexes employing a tetradentate bis-carbene bis-phenolate ligand.

The synthesis of Mn and Cr nitride complexes of a pro-radical tetradentate bis-phenol bis-N-heterocyclic carbene ligand H2LC2O2 was investigated. Employing either azide photolysis of the Mn precursor complex MnLC2O2(N3) or a nitride exchange reaction between MnLC2O2(Br) and the nitride exchange reagent Mnsalen(N) failed to provide a useful route to the target nitride MnLC2O2(N). Experimental results support initial formation of the target nitride MnLC2O2(N), however, the nitride rapidly inserts into a Mn-C bond.

Untangling ancillary ligand donation locus of oxidation effects on metal nitride reactivity.

We detail the relative role of ancillary ligand electron-donating ability in comparison to the locus of oxidation (either metal or ligand) on the electrophilic reactivity of a series of oxidized Mn salen nitride complexes. The electron-donating ability of the ancillary salen ligand was tuned the -phenolate substituent (R = CF, H, Bu, OPr, NMe, NEt) in order to have minimal effect on the geometry at the metal center. Through a suite of experimental (electrochemistry, electron paramagnetic resonance spectroscopy, UV-vis-NIR spectroscopy) and theoretical (density functional theory) techniques, we have demonstrated that metal-based oxidation to [Mn(Sal)N] occurs for R = CF, H, Bu, OPr, while ligand radical formation to [Mn(Sal)N]˙ occurs with the more electron-donating substituents R = NMe, NEt.

Novel perfluoropolyalkylethers monomers: synthesis and photo-induced cationic polymerization.

Unlabelled: Several difunctional oligomers were synthesized by functionalizing perfluoropolyalkylether (PFPAE) chains with different vinyl ethers and epoxides end-groups. Due to their innate synthetic challenges and demanding purification protocols, the PFPAE derivatives were obtained in low yield and with an average functionality lower than 2. However, the functionalized PFPAE oligomers were successful in being used in photo-induced cationic polymerization processes, obtaining transparent and soft films.

Fluorodesulfurization of Thionobenzodioxoles with Silver(I) Fluoride.

Difluorobenzodioxole is an important functional group found in both pharmaceuticals and agrochemicals. The late-stage introduction of this functional group is challenged by typical fluorination conditions of HF and strong oxidants. Here, we demonstrate that a range of difluorobenzodioxoles can be prepared from catechols in two steps through conversion into thionobenzodioxoles, followed by desulfurative fluorination with silver(I) fluoride.