628301-58-6

Upstream product

• 603-35-0 triphenylphosphine 
• 328-74-5 3,5-Bis-(trifluoromethyl)aniline 

Downstream Products

• 1268836-61-8 C₂₁H₈F₁₈N₂ 

Relevant academic research and scientific papers

Electronic Structures and Reactivity Profiles of Aryl Nitrenoid-Bridged Dicopper Complexes

Dicopper complexes templated by dinucleating, pacman dipyrrin ligand scaffolds (Mesdmx, tBudmx: Dimethylxanthine-bridged, cofacial bis-dipyrrin) were synthesized by deprotonation/metalation with mesitylcopper (CuMes; Mes: Mesityl) or by transmetalation with cuprous precursors from the corresponding deprotonated ligand. Neutral imide complexes (Rdmx)Cu2(μ2-NAr) (R: Mes, tBu; Ar: 4-MeOC6H4, 3,5-(F3C)2C6H3) were synthesized by treatment of the corresponding dicuprous complexes with aryl azides. While one-electron reduction of (Mesdmx)Cu2(μ2-N(C6H4OMe)) with potassium graphite initiates an intramolecular, benzylic C-H amination at room temperature, chemical reduction of (tBudmx)Cu2(μ2-NAr) leads to isolable [(tBudmx)Cu2(μ2-NAr)]-product salts. The electronic structures of the thermally robust [(tBudmx)Cu2(μ2-NAr)]0/-complexes were assessed by variable-temperature electron paramagnetic resonance spectroscopy, X-ray absorption spectroscopy (Cu L2,3/K-edge, N K-edge), optical spectroscopy, and DFT/CASSCF calculations. These data indicate that the formally Class IIIA mixed valence complexes of the type [(Rdmx)Cu2(μ2-NAr)]-feature significant NAr-localized spin following reduction from electronic population of the [Cu2(μ2-NAr)] ? manifold, contrasting previous methods for engendering iminyl character through chemical oxidation. The reactivity of the isolable imido and iminyl complexes are examined for prototypical radical-promoted reactivity (e.g., nitrene transfer and H-atom abstraction), where the divergent reactivity is rationalized by the relative degree of N-radical character afforded from different aryl substituents.

Application of electron-withdrawing coordinatively unsaturated η6-arene β-diketiminato-Ruthenium complexes in Lewis acid catalyzed Diels-Alder reactions

Utilizing the aza-Wittig reaction involving the ylid 3,5-(CF 3)2C6H3NPPh3 and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, a highly fluorinated and electron-withdrawing β-diketiminate was obtained. Using strong bases, nBuLi, Ag2O, or TlOEt, the corresponding β-diketiminato-Li, -Ag, or -Tl chelated complexes were prepared. Subsequent in situ transmetalation with (Ru(η6-C6H6)Cl2) 2 or (Ru(η6-p-cymene)Cl2)2 afforded the half-sandwich chloro-substituted Ru(II) β-diketimino complexes in high yield. The synthesis of the Lewis acidic catalysts featuring a vacant coordination site at the metal center was accomplished using [Na]BArF (BArF = tetrakis[3,5-bis(trifluoromethyl)phenyl]boron). These complexes are active for the Lewis acid catalyzed Diels-Alder reaction between α,β-unsaturated aldehydes, that is, methacrolein, acrolein, and dienes, that is, cyclopentadiene and 2,3-dimethyl-1,3-butadiene, with conversions in the range of 66-98% under mild conditions. Whereas the herein described catalysts generally promote exo selectivity of the [4 + 2] cycloaddition between methacrolein and cyclopentadiene, the reaction involving acrolein shows predominantly the formation of the endo adduct, similar to that observed for the noncatalyzed reaction. Importantly, the coordinatively unsaturated complexes demonstrate moderate Lewis acidity, which allows for the controlled reaction between methacrolein and 2,3-dimethyl-1,3-butadiene to 1,3,4-trimethyl-3-cyclohexene-1- carboxaldehyde without further isomerization to the bicyclic ketone, which is in contrast to strong Lewis acidic catalysts based on transition metals or main-group elements reported in the literature.