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Oxidation-induced ambiphilicity triggers N-N bond formation and dinitrogen release in octahedral terminal molybdenum(v) nitrido complexes.

ABSTRACT: Coupling of octahedral, terminal d¹ molybdenum(v) nitrido complexes supported by a dianionic pentadentate ligand via N-N bond formation to give μ-dinitrogen complexes was found to be thermodynamically feasible but faces significant kinetic barriers. However, upon oxidation, a kinetically favored nucleophilic/electrophilic N-N bond forming mechanism was enabled to give monocationic μ-dinitrogen dimers. Computational and experimental evidence for this "oxidation-induced ambiphilic nitrido coupling" mechanism is presented. The factors influencing release of dinitrogen from the resulting μ-dinitrogen dimers were also probed and it was found that further oxidation to a dicationic species is required to induce (very rapid) loss of dinitrogen. The mechanistic path discovered for N-N bond formation and dinitrogen release follows an ECECC sequence (E = "electrochemical step"; C = "chemical step"). Experimental evidence for the intermediacy of a highly electrophilic, cationic d⁰ molybdenum(vi) nitrido in the N-N bond forming mechanism via trapping with an isonitrile reagent is also discussed. Together these results are relevant to the development of molecular catalysts capable of mediating ammonia oxidation to dihydrogen and dinitrogen.

SUBMITTER: Almquist CC

PROVIDER: S-EPMC10988598 | biostudies-literature | 2024 Apr

REPOSITORIES: biostudies-literature

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Oxidation-induced ambiphilicity triggers N-N bond formation and dinitrogen release in octahedral terminal molybdenum(v) nitrido complexes.

Almquist C Christopher CC Rajeshkumar Thayalan T Jayaweera H D A Chathumal HDAC Removski Nicole N Zhou Wen W Gelfand Benjamin S BS Maron Laurent L Piers Warren E WE

Chemical science 20240216 14

Coupling of octahedral, terminal d<sup>1</sup> molybdenum(v) nitrido complexes supported by a dianionic pentadentate ligand <i>via</i> N-N bond formation to give μ-dinitrogen complexes was found to be thermodynamically feasible but faces significant kinetic barriers. However, upon oxidation, a kinetically favored nucleophilic/electrophilic N-N bond forming mechanism was enabled to give monocationic μ-dinitrogen dimers. Computational and experimental evidence for this "oxidation-induced ambiphili ...[more]

PMID: 38577349

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Project description:High valent iron species are very reactive molecules involved in oxidation reactions of relevance to biology and chemical synthesis. Herein we describe iron(iv)-tosylimido complexes [FeIV(NTs)(MePy2tacn)](OTf)2 (1(IV)[double bond, length as m-dash]NTs) and [FeIV(NTs)(Me2(CHPy2)tacn)](OTf)2 (2(IV)[double bond, length as m-dash]NTs), (MePy2tacn = N-methyl-N,N-bis(2-picolyl)-1,4,7-triazacyclononane, and Me2(CHPy2)tacn = 1-(di(2-pyridyl)methyl)-4,7-dimethyl-1,4,7-triazacyclononane, Ts = Tosyl). 1(IV)[double bond, length as m-dash]NTs and 2(IV)[double bond, length as m-dash]NTs are rare examples of octahedral iron(iv)-imido complexes and are isoelectronic analogues of the recently described iron(iv)-oxo complexes [FeIV(O)(L)]2+ (L = MePy2tacn and Me2(CHPy2)tacn, respectively). 1(IV)[double bond, length as m-dash]NTs and 2(IV)[double bond, length as m-dash]NTs are metastable and have been spectroscopically characterized by HR-MS, UV-vis, 1H-NMR, resonance Raman, Mössbauer, and X-ray absorption (XAS) spectroscopy as well as by DFT computational methods. Ferric complexes [FeIII(HNTs)(L)]2+, 1(III)-NHTs (L = MePy2tacn) and 2(III)-NHTs (L = Me2(CHPy2)tacn) have been isolated after the decay of 1(IV)[double bond, length as m-dash]NTs and 2(IV)[double bond, length as m-dash]NTs in solution, spectroscopically characterized, and the molecular structure of [FeIII(HNTs)(MePy2tacn)](SbF6)2 determined by single crystal X-ray diffraction. Reaction of 1(IV)[double bond, length as m-dash]NTs and 2(IV)[double bond, length as m-dash]NTs with different p-substituted thioanisoles results in the transfer of the tosylimido moiety to the sulphur atom producing sulfilimine products. In these reactions, 1(IV)[double bond, length as m-dash]NTs and 2(IV)[double bond, length as m-dash]NTs behave as single electron oxidants and Hammett analyses of reaction rates evidence that tosylimido transfer is more sensitive than oxo transfer to charge effects. In addition, reaction of 1(IV)[double bond, length as m-dash]NTs and 2(IV)[double bond, length as m-dash]NTs with hydrocarbons containing weak C-H bonds results in the formation of 1(III)-NHTs and 2(III)-NHTs respectively, along with the oxidized substrate. Kinetic analyses indicate that reactions proceed via a mechanistically unusual HAT reaction, where an association complex precedes hydrogen abstraction.

Dataset Information

Oxidation-induced ambiphilicity triggers N-N bond formation and dinitrogen release in octahedral terminal molybdenum(v) nitrido complexes.

Publications

Oxidation-induced ambiphilicity triggers N-N bond formation and dinitrogen release in octahedral terminal molybdenum(v) nitrido complexes.

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