Reaction of a copper(I) complex supported by a sterically demanding tripodal tetradentate ligand, HIPT3tren, and O2 gave a mononuclear copper(II) end‐on superoxo complex. Spectroscopic (UV/Vis, resonance Raman, ESR, and 1H‐NMR) and DFT studies have been performed. The O2‐binding process as well as the reaction toward external substrates have been investigated kinetically to demonstrate the unique behavior of the copper(II) end‐on superoxo complex, which may occur as a result of the existence of the hydrophobic core around the copper coordination sphere created by the HIPT3tren ligand.
Nitric oxide dimerization in gas phase and aromatic hosts (benzene) has been investigated with ab initio quantum mechanics. Using the (RO)MP2-aug-cc-pVDZ method, the computed bond dissociation energy (ON...NO) and geometry of (NO)2 in the gas phase are consistent with the reported spectroscopic data. A relatively strong interaction (-5.4 kcal/mol) between (NO)2 and benzene indicates that aromatic surrounding enhances the NO dimerization. Calculations on reactions of phosphine and methanethiol with NO and (NO)2 show that the dimer is much more reactive. This explains reactions of NO with phosphines and thiols.
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