ALKANE FUNCTIONALIZATION AT (MU-OXO)DIIRON(III) CENTERS

The reactivity of (mu-oxo)diferric complexes with (t)BuOOH (TBHP) for the functionalization of alkanes in CH3CN has been investigated as par t of our efforts to model dinuclear sites in nonheme iron enzymes. [Fe 2(TPA)2O(OAc)](ClO4)3(1)(TPA = tris(2-pyridylmethyl)amine, OAc = aceta te) is an efficient catalyst for cyclohexane oxidation, affording cycl ohexanol (A, 9 equiv), cyclohexanone (K, 11 equiv), and (tert-butylper oxy)cyclohexane (P, 16 equiv) in 0.25 h at ambient temperature and pre ssure under an argon atmosphere. The catalyst is remarkably robust, as indicated by the H-1 NMR and UV-vis spectra of the reaction mixture d uring the catalytic reaction and by its ability to maintain its turnov er efficiency with subsequent additions of oxidant. The catalytic mech anism for TBHP utilization was explored by observing the effects of va rying the tripodal ligands on the (mu-oxo)(mu-carboxylato) diferric ca talysts and varying the bridge on Fe2O(TPA)2 catalysts. The (A + K)/P ratio increased as the ligands became more electron donating. Solvent also played an important role in determining the partitioning of produ cts between A + K and P, with benzonitrile favoring hydroxylated produ cts at the expense of P and pyridine having the opposite effect. Most significantly, the addition of dimethyl sulfide (to trap two-electron oxidants) to this system completely suppressed the formation of A and K but did not affect the amount of P formed. These observations demons trate that A and K must derive from an oxidant different from that res ponsible for P production. TBHP is thus decomposed by the catalyst via two mechanisms: a heterolytic process that affords a high-valent iron -oxo species responsible for A and K formation and a homolytic pathway that generates (t)BuO. and (t)BuOO. radicals that are responsible for the formation of P. It is proposed that the heterolytic mechanism is initiated by the dissociation of the bridging anion from one iron cent er to provide a site for coordinating the alkyl peroxide ion. Consiste nt with this notion, the hydrogen abstraction power of the oxidant, as indicated by isotope effects of cyclohexane hydroxylation, is modulat ed by the tripodal ligand but is independent of the bridging anion, al though the affinity of the bridging anion for the (mu-oxo)diferric cen ter plays a role in determining the efficiency of the catalyst in cons uming the alkyl hydroperoxide.