Magnetron sputtering tuned “π back-donation” sites over metal oxides for enhanced electrocatalytic nitrogen reduction

As an environmentally-benign and sustainable option for NH3 synthesis, electrochemical nitrogen reduction reaction (NRR) has been expected to replace the traditional Haber-Bosch process. Transition metals with empty d-orbitals achieve NRR...

A Comprehensive Analysis of the Metal–Nitrile Bonding in an Organo-Diiron System

Nitriles (N≡CR) are ubiquitous in coordination chemistry, yet literature studies on metal–nitrile bonding based on a multi-technique approach are rare. We selected an easily-available di-organoiron framework, containing both π-acceptor (CO, aminocarbyne) and donor (Cp = η5−C5H5) ligands, as a suitable system to provide a comprehensive description of the iron–nitrile bond. Thus, the new nitrile (2–12)CF3SO3 and the related imine/amine complexes (8–9)CF3SO3 were synthesized in 58–83% yields from the respective tris-carbonyl precursors (1a–d)CF3SO3, using the TMNO strategy (TMNO = trimethylamine-N-oxide). The products were fully characterized by elemental analysis, IR (solution and solid state) and multinuclear NMR spectroscopy. In addition, the structures of (2)CF3SO3, (3)CF3SO3, (5)CF3SO3 and (11)CF3SO3 were ascertained by single crystal X-ray diffraction. Salient spectroscopic data of the nitrile complexes are coherent with the scale of electron-donor power of the R substituents; otherwise, this scale does not match the degree of Fe → N π-back-donation and the Fe–N bond energies, which were elucidated in (2–7)CF3SO3 by DFT calculations.

In Search of the Perfect Triple BB Bond: Mechanical Tuning of the Host Molecular Trap for the Triple Bond B≡B Fragment

The coordination of the B2 fragment by two σ-donor ligands L: could lead to a diboryne compound with a formal triple bond L:→B≡B←:L. σ-Type coordination L:→B leads to an excess of electrons around the B2 central fragment, whereas π-back-donation from the B≡B moiety to ligand L has a compensation effect. Coordination of the σ-donor and π-acceptor ligand is accompanied by the lowering of the BB bond order. Here, we propose a new approach to obtain the perfect triple BB bond through the incorporation of the BB unit into a rigid molecular capsule. The idea is the replacement of π-back-donation, as the principal stabilization factor in the linear NBBN structure, with the mechanical stabilization of the BB fragment in the inert molecular capsule, thus preserving the perfect B≡B triple bond. Quantum-chemical calculations show that the rigid molecular capsule provided a linear NBBN structure and an unusually short BB bond of 1.36 Å. Quantum-chemical calculations of the proposed diboryne adducts show a perfect triple bond B≡B without π-back-donation from the B2 unit to the host molecule. Two mechanisms were tested for the molecular design of a diboryne adduct with a perfect B≡B triple bond: the elimination of π-back-donation and the construction of a suitable molecular trap for the encapsulation of the B2 unit. The second factor that could lead to the strengthening or stretching of a selected chemical bond is molecular strain produced by the rigid molecular host capsule, as was shown for B≡B and for C≡C triple bonds. Different derivatives of icosane host molecules exhibited variation in BB bond length and the corresponding frequency of the BB stretch. On the other hand, this group of molecules shows a perfect triple BB bond character and they all possess a similar level of HOMO.

Oxidation of Ethanol in Cu-Faujasites Studied by IR Spectroscopy

In this study, IR studies of the coadsorption of ethanol and CO on Cu+ cations evidenced the transfer of electrons from ethanol to Cu+, which caused the lowering of the frequency of the band attributed to CO bonded to the same Cu+ cation due to the more effective π back donation of d electrons of Cu to antibonding π* orbitals of CO. The reaction of ethanol with acid sites in zeolite HFAU above 370 K produced water and ethane, polymerizing to polyethylene. Ethanol adsorbed on zeolite Cu(2)HFAU containing acid sites and Cu+exch also produced ethene, but in this case, the ethene was bonded to Cu+ and did not polymerize. C=C stretching, which is IR non-active in the free ethene molecule, became IR active, and a weak IR band at 1538 cm−1 was present. The reaction of ethanol above 370 K in Cu(5)NaFAU zeolite (containing small amounts of Cu+exch and bigger amounts of Cu+ox, Cu2+exch and CuO) produced acetaldehyde, which was further oxidized to the acetate species (CH3COO-). As oxygen was not supplied, the donors of oxygen were the Cu species present in our zeolite. The CO and NO adsorption experiments performed in Cu-zeolite before and after ethanol reaction evidenced that both Cu+ox and Cu2+ (Cu2+exch and CuO) were consumed by the ethanol oxidation reaction. The studies of the considered reaction of bulk CuO and Cu2O as well as zeolites, in which the contribution of Cu+ox species was reduced by various treatments, suggest that ethanol was oxidized to acetaldehyde by Cu2+ox (the role of Cu+ox could not be elucidated), but Cu+ox was the oxygen donor in the acetate formation.