Henning Broda

Free Reaction Enthalpy Profile of the Schrock Cycle Derived from Density Functional Theory Calculations on the Full [MoHIPTN3N] Catalyst

A series of density functional theory (DFT) calculations on the full [Mo(HIPT)N3N] catalyst are performed to obtain an energy profile of the Schrock cycle. This is a continuation of our earlier investigation of this cycle in which the bulky hexaisopropyterphenyl (HIPT) substituents of the ligand were replaced by hydrogen atoms (Angew. Chem., Int. Ed. 2005, 44, 5639). In an effort to provide a treatment that is as converged as possible from a quantum-chemical point of view, the present study now fully takes the HIPT moieties into account. Moreover, structures and energies are calculated with a near-saturated basis set, leading to models with 280 atoms and 4850 basis functions. Solvent and scalar relativistic effects have been treated using the conductor-like screening model and zeroth-order regular approximation, respectively. Free reaction enthalpies are evaluated using the PBE and B3LYP functionals. A comparison to the available experimental data reveals much better agreement with the experiment than preceding DFT treatments of the Schrock cycle. In particular, free reaction enthalpies of reduction steps and NH3/N2 exchange are now excellently reproduced.

Reduction and Protonation of Mo(IV) Imido Complexes with depe Coligands: Generation and Reactivity of a S = 1/2 Mo(III) Alkylnitrene Intermediate

Reduction and protonation of Mo(IV) imido complexes with diphosphine coligands constitutes the second part of the Chatt cycle for biomimetic reduction of N2 to ammonia. In order to obtain insights into the corresponding elementary reactions we synthesized the Mo(IV) ethylimido complex [Mo(CH3CN)(NEt)(depe)2](OTf)2 (2-MeCN) from the Mo(IV)-NNH2 precursor [Mo(NNH2)(OTf)(depe)2](OTf) (1). As shown by UV-vis and NMR spectroscopy, exchange of the acetonitrile ligand with one of the counterions in THF results in formation of the so far unknown complex [Mo(OTf)(NEt)(depe)2](OTf) (2-OTf). 2-MeCN and 2-OTf are studied by spectroscopy and X-ray crystallography in conjunction with DFT calculations. Furthermore, both complexes are investigated by cyclic voltammetry and spectroelectrochemistry. The complex 2-OTf undergoes a two-electron reduction in THF associated with loss of the trans ligand triflate. In contrast, 2-MeCN in acetonitrile is reduced to an unprecedented Mo(III) alkylnitrene complex [Mo(NEt)(CH3CN)(depe)2]OTf (5) which abstracts a proton from the parent Mo(IV) compound 2-MeCN, forming the Mo(III) ethylamido complex 5H and a Mo(II) azavinylidene complex 6. Compound 5 is also protonated to the Mo(III) ethylamido complex 5H in the presence of externally added acid and further reduced to the Mo(II) ethylamido complex 7. The results of this study provide further support to a central reaction paradigm of the Schrock and Chatt cycles: double reductions (and double protonations) lead to high-energy intermediates, and therefore, every single reduction has to be followed by a single protonation (and vice versa). Only in this way the biomimetic conversion of dinitrogen to ammonia proceeds on a minimum-energy pathway.

Recent developments in synthetic nitrogen fixation

Within the background of biological nitrogen fixation mediated by the enzyme nitrogenase, transition-metal complexes capable of binding and activating dinitrogen towards protonation and reduction have been synthesised. Of particular interest in this research area has been the transition-metal mediated conversion of dinitrogen to ammonia (stoichiometric and catalytic) and the elucidation of the corresponding mechanistic pathways. The present review summarises recent studies in this field. To this end, the available complexes binding N2 and/or its intermediates on the pathway to ammonia are subdivided into systems containing early transition metals, Mo & W, iron and late transition metals. The implications of the findings obtained on low-molecular weight compounds with respect to the functionalisation of N2 and the reduction of N2 to ammonia on the FeMoco of nitrogenase are considered.