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. 2018 Jan 23;54(8):892-895.
doi: 10.1039/c7cc08619a.

Phenylamino derivatives of tris(2-pyridylmethyl)amine: hydrogen-bonded peroxodicopper complexes

Affiliations

Phenylamino derivatives of tris(2-pyridylmethyl)amine: hydrogen-bonded peroxodicopper complexes

E W Dahl et al. Chem Commun (Camb). .

Abstract

A series of copper complexes bearing new 6-substituted tris(2-pyridylmethyl)amine ligands (LR) appended with NH(p-R-C6H4) groups (R = H, CF3, OMe) were prepared. These ligands are electronically tunable (ΔE1/2 = 160 mV) and CuI(LR)+ complexes react with oxygen to form hydrogen bonded (trans-1,2-peroxo)dicopper species.

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Figures

Figure 1
Figure 1
CuICl complexes derived from H3thpa and LR (A). Cyclic voltammetry of 1H, 1CF3 and 1OMe ((B) 0.1 M NBu4PF6 CH2Cl2). Crystal structure of 1H ((C) 30% ellipsoids, H atoms not involved in H-bonding omitted for clarity).
Figure 2
Figure 2
Reactivity of Cu(I) complexes toward O2 (A). Crystal structure of 2H ((B) 30% ellipsoids, some atoms represented in wireframe, H atoms not involved in H-bonding and BAr’ counteranions omitted for clarity).
Figure 3
Figure 3
UV-Vis overlay of 2H, 2CF3, 2OMe (1:1 CH2Cl2/acetone, −70°C), and the reaction of [Cu(tpaOPh)]BAr’ with O2 at −70°C. Inlay shows λmax of O to Cu LMCT in 2R.

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