File(s) not publicly available
Reaction of H2 with a Binuclear Zirconium Dinitrogen Complex - Evaluation of Theoretical Models and Hybrid Approaches
journal contributionposted on 2023-05-16, 18:50 authored by Brian YatesBrian Yates, Basch, H, Musaev, DG, Morokuma, K
Molecular orbital and hybrid ONIOM (both IMOMO and IMOMM) calculations have been carried out on the important reaction of H2 with a binuclear zirconium dinitrogen complex to test the efficacy of several structural models of the ancillary ligand. The complete experimental ligand, PhP(CH 2SiMe2NSiMe2CH2)2PPh, in the zirconium complex has been treated at the IMOMM level, while two smaller approximations of the ligand, HP(CH2SiH2NSiH 2CH2)2PH and (PH3) 2(NH2)2, have received the full molecular orbital treatment. The mechanism of dihydrogen addition has been compared with our earlier study (Basch, Musaev, and Morokuma J. Am. Chem. Soc. 1999, 121, 5754-5761). We find that the substituent effects do cause some small changes in both the structures of the complexes studied and the activation energies of the transition structures. However for the most part the potential energy profiles are very similar to our earlier study and lend support to our use of simple theoretical models to represent moderately large experimental structures. Â© 2006 American Chemical Society.
Publication titleJournal of Chemical Theory and Computation
Department/SchoolSchool of Natural Sciences
PublisherAmerican Chemical Society
Place of publicationWashington