Interplay of Electronic Cooperativity and Exchange Coupling in Regulating the Reactivity of Diiron(IV)-oxo Complexes towards C-H and O-H Bond Activation.
作者： Azaj Ansari , Mursaleem Ansari , Asmita Singha , Gopalan Rajaraman
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摘要: Activation of inert C-H bonds such as those methane are extremely challenging for chemists but in the nature, soluble monooxygenase enzyme readily oxidize to methanol using a diiron(IV) species. This has prompted look similar model systems. Recently (μ-oxo)bis(μ-carboxamido)diiron(IV) ([Fe(IV)2O(L)2]2+ L= N,N-bis-(3ʹ,5ʹ-dimethyl-4ʹ-methoxypyridyl-2ʹ-methyl)-Nʹ-acetyl- 1,2-diaminoethane) complex been generated via bulk electrolysis and this species activates an bond almost 1000 times faster compared mononuclear Fe(IV)=O at same time selectively O-H alcohols. Herein DFT calculations, we have studied electronic spectral features diiron {Fe(III)-μ(O)-Fe(III)} (complex I), {Fe(III)-μ(O)-Fe(IV)} (II) {Fe(IV)-μ(O)-Fe(IV)} (III) complexes. Strong antiferromagnetic coupling computed, leads spin-coupled S=0, S=3/2 S=0 ground states I-III respectively. The mechanistic study activation reveals multi-state reactivity scenario where is found occur S=4. on other hand, occurs S=2 spin coupled state corresponding intermediate individual Fe(IV) centers. Significant cooperativity between two metal centers during course reaction witnessed unfolds reason behind efficiency selectivity observed.
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