Abstract:
:Copper(II) complexes supported by N3-tridentate ligands, consisting of a rigid cyclic diamine (8-membered cyclic-diamine; L8 or 7-membered cyclic-diamine; L7) and a 2-(2-pyridyl)ethyl (-CH2CH2Py) group, were synthesized and structurally characterized. Reaction of the copper(II) complexes and cumene hydroperoxide (CmOOH) in the presence of triethylamine in CH3CN gave the corresponding cumylperoxide complexes L8CuIIOOCm and L7CuIIOOCm. The UV-vis and EPR spectra suggested that L8CuIIOOCm takes a tetrahedrally distorted structure, whereas L7CuIIOOCm has a planar geometry in solution. Resonance Raman spectra of these alkylperoxide complexes indicated that the O-O stretching vibration energy of L8CuIIOOCm (νO-O=878cm-1) is somewhat lower than that of L7CuIIOOCm (νO-O=881cm-1). Such a difference in O-O bond strength is reflected to the reactivity difference of these two alkylperoxide complexes. Namely, the reactivity L8CuIIOOCm toward CHD (1,4-cyclohexadiene) as well as solvent molecule (CH3CN) is higher than that of L7CuIIOOCm due to the weaker O-O bond of the former complex as compared to that of the latter complex. Geometric effects on the reactivity induced by the supporting ligands are discussed.
journal_name
J Inorg Biochemjournal_title
Journal of inorganic biochemistryauthors
Abe T,Morimoto Y,Mieda K,Sugimoto H,Fujieda N,Ogura T,Itoh Sdoi
10.1016/j.jinorgbio.2017.08.016subject
Has Abstractpub_date
2017-12-01 00:00:00pages
375-383eissn
0162-0134issn
1873-3344pii
S0162-0134(17)30223-4journal_volume
177pub_type
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