4.7 Article

Electrostatic polarization of nonpolar substrates: a study of interactions between simple cations and Mo-bound N2

期刊

DALTON TRANSACTIONS
卷 48, 期 29, 页码 11004-11017

出版社

ROYAL SOC CHEMISTRY
DOI: 10.1039/c9dt01606f

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资金

  1. Wyoming NASA Space Grant Consortium [NNX15AK56A]
  2. Institutional Development Award (IDeA) from the National Institute of General Medical Health Sciences of the National Institutes of Health [2P20GM103432]
  3. National Science Foundation [CHE-0619920, CHE-1358498, CHE-1147542, CHE-1762161, CHE-1566622, CHE-1213903]
  4. UW Office of Vice President of Research
  5. UW School of Energy Resources
  6. UW Department of Chemistry
  7. Wyoming Research Scholars Program

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Although a great deal of catalytic studies have focused on covalent interactions between substrates and catalyst centers, recognition of the importance of noncovalent and ionic interactions is driving new approaches to catalyst design. Electrostatic interactions with simple cations (those with little covalency, such as alkali metals) play crucial roles in many catalytic processes, but these effects are challenging to study due to their complicated solvation and speciation behaviour. These effects are particularly difficult to study during cation-mediated reactions with weakly-polar or non-polar substrates. Dinitrogen is one of the most nonpolar substrates known to be affected by electrostatic interactions in both heterogeneous and homogeneous reactions but understanding the significance of these effects requires further exploration. To examine these effects systematically, a new multidentate ligand framework bearing pendent crown ethers has been developed and incorporated into a series of Mo(0)-based dinitrogen complexes. Prepared via both reduction and ligand substitution routes, the strength and impact of cation-N-2 interactions have been studied experimentally (IR spectroscopy) and computationally. Although the smallest cation (Li+) has the largest impact on the ground-state heterobimetallic activation of N-2, solvation interactions are highly competitive and result in low Li+-(N-2)Mo binding affinities. Thus, although smaller cations can have the largest electronic impact on substrates, these interactions are also the least persistent.

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