Mechanistic Studies on Programmed C—O/C—H Activation with Valence-Adjusted Ti-Complexes

Two-electron reduction of[N_(2)NBn]Ti^(Ⅳ)Cl2(3)gave a highly reactive[N_(2)N]Ti^(Ⅱ)species,which underwent C—O bond activation of THF(tetrahydrofuran)to generate[N2NBn]Ti^(Ⅳ)[O(CH2)4](4)through oxidative addition.The resulted Ti^(Ⅳ)-Csp^(3)bond in oxametallacyclo-hexane was tantamount to the elaborately-designed Ti-alkyl complexes,competent to activate intramolecular Csp^(2)-H bond,forming ortho-cyclometalated complex[N_(2)NCH_(2)C_(6)H_(4)]Ti^(Ⅳ)(O^(n)Bu)(5).Key intermediates were isolated and fully characterized by X-ray crystal-lography.Mechanistic studies revealed that the oxidative addition of C-O bond took place at Ti^(Ⅱ)-center via a radical intermediate,while a Csp^(2)-H bond activation proceeded byσ-bond metathesis with a kitelike four-centered Ti^(Ⅳ)-transition state.

Photo-induced deep aerobic oxidation of alkyl aromatics

Oxidation is a major chemical process to produce oxygenated chemicals in both nature and the chemical industry.Presently,the industrial manufacture of benzoic acids and benzene polycarboxylic acids(BPCAs)is mainly based on the deep oxidation of polyalkyl benzene,which is somewhat suffering from environmental and economical disadvantage due to the formation of ozone-depleting Me Br and corrosion hazards of production equipment.In this report,photo-induced deep aerobic oxidation of(poly)alkyl benzene to benzene(poly)carboxylic acids was developed.CeCl_(3) was proved to be an efficient HAT(hydrogen atom transfer)catalyst in the presence of alcohol as both hydrogen and electron shuttle.Dioxygen(O_(2))was found as a sole terminal oxidant.In most cases,pure products were easily isolated by simple filtration,implying large-scale implementation advantages.The reaction provides an ideal protocol to produce valuable fine chemicals from naturally abundant petroleum feedstocks.

A mixed-valent high spin(μ-hydroxo)dicobalt(Ⅱ/Ⅲ) complex and its end-on type dioxygen adduct: synthesis, geometric and electronic structure studies

A mixed-valent high spin (μ-hydroxo)dicobalt(Ⅱ/Ⅲ) complex bearing N,N′-bis(5-tertbutylsalicylidene)-1,2-diaminobenzene(Salophen^(tBu)) ligand was synthesized by reacting (Salophen^(tBu))Co(Ⅱ)(Py) with O_(2) at low temperature.This complex was isolated and structurally characterized by single crystal X-ray diffraction and infrared spectrum.Magnetic measurement showed a quartet ground state for this complex at room temperature,which was also supported by electron paramagnetic resonance (EPR)characterization.Computational investigations indicated the deviation of the equatorial N_(2)O_(2) coordination geometry around the Co(Ⅱ) center from plane stabilized the quartet state.The end-on type O_(2) adduct of this (μ-hydroxo)dicobalt(Ⅱ/Ⅲ) complex was isolated as dark-brown crystals and structurally and spectroscopically characterized.EPR measurement of this compound in solid state at room temperature presented an isotropic singlet at g~2,revealing the superoxide-like electronic feature of the coordinated O_(2) and was in line with the calculation results.The reactivity of the Co(Ⅲ)-O_(2) complex with N-hydroxyphthalimide,which can act as hydrogen atom donor,was also examined.