Low-valent group 6 metals/Al(CF) donor-acceptor systems for CO activation and cleavage.

Donor-acceptor systems for CO activation combining a formally zero-valent group 6 metal as the donor with the Lewis acid Al(CF) (AlCF) are reported. They were obtained from AlCF adducts of N-complexes by N-to-CO substitution. One species was capable of C-O cleavage.

Nitrogen Fixation by Manganese Complexes - Waiting for the Rush?

Manganese is currently experiencing a great deal of attention in homogeneous catalysis as a sustainable alternative to platinum group metals due to its abundance, affordable price and low toxicity. While homogeneous nitrogen fixation employing well-defined transition metal complexes has been an important part of coordination chemistry, manganese derivatives have been only sporadically used in this research area. In this contribution, the authors systematically cover manganese organometallic chemistry related to N activation spanning almost 60 years, identify apparent pitfalls and outline encouraging perspectives for its future development.

An Experimental and Computational Investigation Rules Out Direct Nucleophilic Addition on the N Ligand in Manganese Dinitrogen Complex [Cp(CO) Mn(N )].

We have re-examined the reactivity of the manganese dinitrogen complex [Cp(CO) Mn(N )] (1, Cp=η -cyclopentadienyl, C H ) with phenylithium (PhLi). By combining experiment and density functional theory (DFT), we have found that, unlike previously reported, the direct nucleophilic attack of the carbanion onto coordinated dinitrogen does not occur. Instead, PhLi reacts with one of the CO ligands to provide an anionic acylcarbonyl dinitrogen metallate [Cp(CO)(N )MnCOPh]Li (3) that is stable only below -40 °C.

Assessing Combinations of B(C F ) and N -Derived Molybdenum Nitrido Complexes for Heterolytic Bond Activation.

Two different dinitrogen-derived molybdenum nitrido complexes varying by their geometry, ligand spheres and oxidations states were shown to engage their N ligand in dative bonding with the strong Lewis acid B(C F ) . The stable adducts were assessed for frustrated Lewis pair-type heterolytic E-H bond splitting of hydrosilanes (E=Si) and HB(C F ) . Whereas Si-H bond activation was achieved, HB(C F ) was shown to substitute B(C F ) in a quantitative or equilibrated fashion, depending on the nature of the nitrido complex.