Research Experiences for Undergraduates in Computational Methods with Applications in Materials Science
MSU Affiliation
College of Arts and Sciences; Department of Chemistry; Center for Computational Sciences
Research Mentor
Charles Edwin Webster
Creation Date
8-2-2024
Abstract
Alkylidyne complexes have garnered significant interest for advances in catalysis in various industrial processes, such as Fischer-Tropsch synthesis and alkyne metathesis. Recently, the alkylidyne complex [N3N]MoCH was synthesized by reacting [N3N]MoCI with lithiated methanoanthracene. Despite the structural similarity between norbornadiene and methanoanthracene, as well as the overall exergonic nature of the reactions, the reaction ony proceeds experimental with lithiated methanoanthracene. To shed light on this transformation, which involves multiple spin states of various short-lived intermediates, we report a computational study elucidating the structure-reactivity relationship of lithiated cyclic reagents. The reaction proceeds through a transmetallation step followed by an endergonic carbon transfer. The carbon transfer is expected to occur via a stepwise mechanism, breaking two C-C bonds separately. The short-lived intermediate after transmetallation can potentially be observed through absorption spectroscopy; thus, simulated spectra and Natural Transition Orbital (NTO) analysis are performed for reference. The proposed mechanism from the computational results suggests a switch in spin states from triplet to singlet during the reaction. We extend our study by examining the reaction between a molybdenum complex wth a pyridine-based PNP pincer ligand (PNP = 2,5-bis(di-tert-butylphosphinomethyl)pyrrolide) and lithiated methanoanthracene.
Presentation Date
Summer 8-2-2024
Keywords
alkylidyne complex, spectroscopy
Recommended Citation
Wahlin, Niles; Le, Nghia; and Webster, Charles Edwin, "Alkylidyne Molybdenum formation from Lithiated Transmetalation: A Computational Insight" (2024). Research Experiences for Undergraduates in Computational Methods with Applications in Materials Science. 10.
https://scholarsjunction.msstate.edu/ccs-reu/10
