Search

Thecomplex Ag3(μ2-3,5-(CF3)2PyrPy)3(3,5-(CF3)2PyrPy= 2,2′-pyridylpyrrolide(1−) ligand) catalyticallypromotes the insertion of the carbene of ethyl diazoacetate (EDA),at room temperature, into the CC bond of a series of arenesto ultimately ring-open them and form the corresponding cycloheptatrienes.In one case, the norcaradiene intermediate can be isolated, whileregioselective CC insertion can be promoted with certain arenesubstrates. The mechanism of CC insertion, preference overC–H insertion, and origin of CC regioselectivity hasbeen probed by a combination of experimental and theoretical studies. [ABSTRACT FROM AUTHOR]

The fluorinated 1,3,5-triazapentadienyl ligands [N{(C3F7)C(2-(NO2)C6H4)N}2]−, [N{(C3F7)C(4-(NO2)C6H4)N}2]−, [N{(C3F7)C(2-(CF3)C6H4)N}2]−, and[N{(C3F7)C(2-F,6-(CF3)C6H3)N}2]−have been used assupporting ligandsin copper(I) ethylene chemistry. [N{(C3F7)C(2-(NO2)C6H4)N}2]Cu(C2H4) (7), [N{(C3F7)C(4-(NO2)C6H4)N}2]Cu(C2H4) (8), [N{(C3F7)C(2-(CF3)C6H4)N}2]Cu(C2H4) (9), and [N{(C3F7)C(2-F,6-(CF3)C6H3)N}2]Cu(C2H4) (10) are easily isolable,thermally stable solidsand display their ethylene proton and carbon resonances in the δ3.68–3.48 and 85.2–87.6 ppm regions, respectively. X-raycrystal structures reveal that 7–10feature trigonal-planar copper sites and κ2-bonded,U-shaped triazapentadienyl ligands. The Cu(I) carbonyl adducts [N{(C3F7)C(2-(NO2)C6H4)N}2]Cu(CO)(NCCH3) (16) and [N{(C3F7)C(4-(NO2)C6H4)N}2]Cu(CO)(NCCH3) (17) have alsobeen synthesized, and they have pseudotetrahedral copper sites. TheCO stretching frequencies of the compounds 16and 17and ethylene 13C NMR chemical shift data of 7–10suggest that these molecules haverather acidic copper sites and weakly donating triazapentadienyl ligands. [ABSTRACT FROM AUTHOR]