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The single\u2010crystal X\u2010ray structure of [Ni(L3)(CH<jats:sub>3<\/jats:sub>CN)](BPh<jats:sub>4<\/jats:sub>)<jats:sub>2<\/jats:sub> reveals that the nickel(II) center is located in a distorted octahedral coordination geometry constituted by all the five nitrogen atoms of the pentadentate ligand and an acetonitrile molecule. In a dichloromethane\/acetonitrile solvent mixture, all the complexes show ligand field bands in the visible region characteristic of an octahedral coordination geometry. They exhibit a one\u2010electron oxidation corresponding to the Ni<jats:sup>II<\/jats:sup>\/Ni<jats:sup>III<\/jats:sup> redox couple the potential of which depends upon the ligand donor functionalities. The new complexes catalyze the oxidation of cyclohexane in the presence of <jats:italic>m<\/jats:italic>\u2010CPBA as oxidant up to a turnover number of 530 with good alcohol selectivity (A\/K, 7.1\u201310.6, A=alcohol, K=ketone). Upon replacing the pyridylmethyl arm in [Ni(L1)(CH<jats:sub>3<\/jats:sub>CN)](BPh<jats:sub>4<\/jats:sub>)<jats:sub>2<\/jats:sub> by the strongly \u03c3\u2010bonding but weakly \u03c0\u2010bonding imidazolylmethyl arm as in [Ni(L5)(CH<jats:sub>3<\/jats:sub>CN)](BPh<jats:sub>4<\/jats:sub>)<jats:sub>2<\/jats:sub> or the sterically demanding 6\u2010methylpyridylmethyl ([Ni(L3)(CH<jats:sub>3<\/jats:sub>CN)](BPh<jats:sub>4<\/jats:sub>)<jats:sub>2<\/jats:sub> and the quinolylmethyl arms ([Ni(L4)(CH<jats:sub>3<\/jats:sub>CN)](BPh<jats:sub>4<\/jats:sub>)<jats:sub>2<\/jats:sub>, both the catalytic activity and the selectivity decrease. DFT studies performed on cyclohexane oxidation by complexes <jats:bold>1<\/jats:bold> and <jats:bold>5<\/jats:bold> demonstrate the two spin\u2010state reactivity for the high\u2010spin [(N5)Ni<jats:sup>II<\/jats:sup>\uf8ffO<jats:sup>.<\/jats:sup>] intermediate (ts1<jats:sub>hs<\/jats:sub>, ts2<jats:sub>doublet<\/jats:sub>), which has a low\u2010spin state located closely in energy to the high\u2010spin state. The lower catalytic activity of complex <jats:bold>5<\/jats:bold> is mainly due to the formation of thermodynamically less accessible <jats:italic>m<\/jats:italic>\u2010CPBA\u2010coordinated precursor of [Ni<jats:sup>II<\/jats:sup>(L5)(OOCOC<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub>Cl)]<jats:sup>+<\/jats:sup> (<jats:bold>5\u2009a<\/jats:bold>). Adamantane is oxidized to 1\u2010adamantanol, 2\u2010adamantanol, and 2\u2010adamantanone (3\u00b0\/2\u00b0, 10.6\u201311.5), and cumene is selectively oxidized to 2\u2010phenyl\u20102\u2010propanol. The incorporation of sterically hindering pyridylmethyl and quinolylmethyl donor ligands around the Ni<jats:sup>II<\/jats:sup> leads to a high 3\u00b0\/2\u00b0 bond selectivity for adamantane oxidation, which is in contrast to the lower cyclohexane oxidation activities of the complexes.<\/jats:p>","DOI":"10.1002\/chem.201402391","type":"journal-article","created":{"date-parts":[[2014,8,5]],"date-time":"2014-08-05T15:58:41Z","timestamp":1407254321000},"page":"11346-11361","source":"Crossref","is-referenced-by-count":89,"title":["Nickel(II) Complexes of Pentadentate N5 Ligands as Catalysts for Alkane Hydroxylation by Using <i>m<\/i>\u2010CPBA as Oxidant: A Combined Experimental and Computational 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