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Copper(I)–Dioxygen Reactivity in the Isolated Cavity of a Nanoscale Molecular Architecture
Author(s) -
Paria Sayantan,
Morimoto Yuma,
Ohta Takehiro,
Okabe Shinsuke,
Sugimoto Hideki,
Ogura Takashi,
Itoh Shinobu
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201800029
Subject(s) - chemistry , trigonal bipyramidal molecular geometry , ligand (biochemistry) , copper , reactivity (psychology) , electron paramagnetic resonance , tripodal ligand , molecule , inorganic chemistry , crystallography , amine gas treating , photochemistry , medicinal chemistry , polymer chemistry , organic chemistry , medicine , biochemistry , physics , receptor , alternative medicine , pathology , nuclear magnetic resonance
Copper(I) and copper(II) complexes supported by a bulky tetradentate N 4 ligand, [Cu I (TIPT 3 tren)(CH 3 CN)]ClO 4 ( 1 ) and [Cu II (TIPT 3 tren)Cl]BF 4 ( 2 ), were synthesized and characterized, where TIPT is 2,2′′,6,6′′‐tetraisopropyl‐1,3′:5′,1′′‐terphenyl and tren is tris(2‐aminoethyl)amine. The copper(II) chloride complex 2 exhibits a trigonal‐bipyramidal structure, as usually observed for the tren ligand system, in which the chloride ligand occupies an axial position and is encapsulated in an isolated cavity consisting of three TIPT substituents. Such a trigonal‐bipyramidal structure is stabilized in acetone, in which hydrogen‐bonding interactions between the anilino N–H groups and the oxygen atom of the acetone molecules, entrapped in the hydrophobic clefts between the TIPT substituents, play an important role. The reaction of copper(I) complex 1 and O 2 in an acetone‐containing solvent at –110 °C gave end‐on copper(II) superoxide complex 3 together with putative side‐on copper(III) peroxide complex 4 , as was evident from detailed studies by variable‐temperature UV/Vis, resonance Raman, and 1 H and 2 H NMR spectroscopy. The formation of 3 and 4 was also validated by DFT calculations.