Predicting the cis -trans dichloro configuration of group 15-16 chelated ruthenium olefin metathesis complexes: A DFT and experimental study

Charles E. Diesendruck, Eyal Tzur, Amos Ben-Asuly, Israel Goldberg, Bernd F. Straub, N. Gabriel Lemcoff

Research output: Contribution to journalArticlepeer-review

87 Scopus citations

Abstract

Gradient-corrected (BP86) and hybrid (M06-L) density functional calculations were used to study the relative stability of cis and /rans-dichloro X-chelated benzylldene ruthenium complexes (X = O, S, Se, N, P). Calculations In the gas phase differed from experimental results, predicting the /rans-dichloro configuration as being more stable In every case. The addition of Poisson-Boltzmann (PBF) continuum approximation (dlchloromethane) corrected the disagreement and afforded energies consistent with experimental results. Novel N, Se, and P chelated ruthenium olefin metathesis complexes were synthesized to evaluate calculation predictions. These findings reinforce the Importance of including solvent corrections In DFT calculations of ruthenium metathesis catalysts and predict that stronger σ donors as chelating atoms tend to electronically promote the unusual and less active cis-dichloro configuration.

Original languageEnglish
Pages (from-to)10819-10825
Number of pages7
JournalInorganic Chemistry
Volume48
Issue number22
DOIs
StatePublished - 16 Nov 2009

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