Computationally designed zirconium organometallic catalyst for direct epoxidation of alkenes without allylic H atoms: aromatic linkage eliminates formation of inert octahedral complexes

  • Bo Yang
  • Thomas A. ManzEmail author
Regular Article


We used density functional theory to computationally design a Zr organometallic catalyst for selectively oxidizing substrates using molecular oxygen as oxidant without coreductant. Each selective oxidation cycle involves four general steps: (a) a peroxo or weakly adsorbed O2 group releases an O atom to substrate to form substrate oxide and an oxo group, (b) an oxygen molecule adds to the oxo group to generate an η2-ozone group, (c) the η2-ozone group rearranges to form an η3-ozone group, and (d) the η3-ozone group releases an O atom to substrate to form substrate oxide and regenerate the peroxo or weakly adsorbed O2 group. This catalyst could potentially be synthesized via the condensation reaction Zr(N(R)R′)4 + 2 C6H4–1,6-(N(C6H3–2′,6′-(CH(CH3)2)2)OH)2 → Zr(C6H4–1,6-(N(C6H3–2′,6′-(CH(CH3)2)2)O)2)2 [aka Zr_Benzol catalyst] + 4 N(R)(R′)H where R and R′ are CH3, CH2CH3, or other alkyl groups. For direct ethylene epoxidation, the computed enthalpic energetic span (i.e., effective activation energy for the entire catalytic cycle) is 27.1 kcal/mol, which is one of the lowest values for catalysts studied to date. We study reaction mechanisms and the stability of different catalyst forms as a function of the oxygen atom chemical potential. Notably, an aromatic linkage in each ligand prevents this catalyst from deactivating to form an inactive octahedral-like structure that contains the same atoms as the dioxo complex, Zr(Ligand)2(O)2. Due to a side reaction that can transfer an allylic H atom from alkene to catalyst, this catalyst is useful for directly epoxidizing alkenes such as ethylene that do not contain allylic H atoms. To better understand the reaction chemistry, we computed net atomic charges and bond orders for the two catalytically relevant reaction cycles. These results quantify electron transfer and bond forming and breaking during the catalytic process.


Ethylene epoxidation Ethylene oxide Computational catalysis Selective oxidation Alkene epoxidation Organometallic complexes 



Supercomputing resources were provided by the Extreme Science and Engineering Discovery Environment (XSEDE). XSEDE is funded by NSF grant OCI-1053575. XSEDE project grant TG-CTS100027 provided allocations on the Stampede cluster at the Texas Advanced Computing Center (TACC) and the Trestles and Comet clusters at the San Diego Supercomputing Center (SDSC). The authors sincerely thank the technical support staff of XSEDE, TACC, and SDSC. The authors also thank Dr. Karen Goldberg and Wilson Bailey for useful discussions regarding the proposed catalyst synthesis reaction.

Compliance with ethical standards

Conflict of interest

The authors and NMSU’s Office of Intellectual Property (Arrowhead Center, Inc.) have applied for a patent on some of the results described in this paper.

Supplementary material

214_2015_1789_MOESM1_ESM.pdf (11.2 mb)
Online Resource 1: DFT-optimized geometries and energies; imaginary frequency for each transition state; triplet-quintet crossing curves for O2 addition to the oxo complex; table of computed relative energies (ESCF, EZP, H, and G) for the Zr_Benzol catalyst with various oxygen-comprised adsorbates; table of assigned spin magnetic moments for triplet complexes; junior and master catalytic cycles and relative energy profiles for direct propene epoxidation using the Zr_Benzol catalyst. (PDF 11509 kb) (2.3 mb)
Online Resource 2: A 7z format archive containing .xyz files (which can be read using any text editor or the free Jmol visualization program downloadable from containing net atomic charges, bond orders, and atomic spin moments (for spin-polarized systems) for all of the DFT-optimized geometries. (ZIP 2322 kb)


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Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  1. 1.Department of Chemical and Materials EngineeringNew Mexico State UniversityLas CrucesUSA

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