Organometallics cover and Research Article

The newest issue of Organometallics, with the theme “Sustainable Organometallic Chemistry” features a cover designed by our own Kathrin H. Hopmann, alongside Jennifer V. Obligacion and Jeff H. Ward. Hopmann and Obligacion present the issue as editors.

The research papers presented in the issue include Ashot Gevorgyan’s article on Buchwald–Hartwig aminations in lipid solvents, an article on Low-valent molybdenum PNP pincer complexes by our CO₂PERATE collaborators at LIKAT, Germany, and a new research article by Ljiljana Pavlovic on enamides hydrogenation:

The article, titled “Cobalt-Catalyzed Asymmetric Hydrogenation of Enamides: Insights into Mechanisms and Solvent Effects” is a collaboration with the group of Paul J. Chirik at Princeton University, USA. It focuses on “the mechanistic details of the (^PhBPE)Co-catalyzed asymmetric hydrogenation of enamides”.

Abstract:
The mechanistic details of the (^PhBPE)Co-catalyzed asymmetric hydrogenation of enamides are investigated using computational and experimental approaches. Four mechanistic possibilities are compared: a direct Co(0)/Co(II) redox path, a metathesis pathway, a nonredox Co(II) mechanism featuring an aza-metallacycle, and a possible enamide–imine tautomerization pathway. The results indicate that the operative mechanism may depend on the type of enamide. Explicit solvent is found to be crucial for the stabilization of transition states and for a proper estimation of the enantiomeric excess. The combined results highlight the complexity of base-metal-catalyzed hydrogenations but do also provide guiding principles for a mechanistic understanding of these systems, where protic substrates can be expected to open up nonredox hydrogenation pathways.