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Non-redox oxy-insertion via organometallic Baeyer-Villiger transformations: A computational Hammett study of platinum(II) complexes

Organometallics, ISSN: 0276-7333, Vol: 30, Issue: 14, Page: 3779-3785
2011
  • 36
    Citations
  • 0
    Usage
  • 14
    Captures
  • 1
    Mentions
  • 0
    Social Media
Metric Options:   Counts1 Year3 Year

Metrics Details

  • Citations
    36
    • Citation Indexes
      36
  • Captures
    14
  • Mentions
    1
    • News Mentions
      1
      • News
        1

Most Recent News

Catalytic synthesis of phenols with nitrous oxide

Nature, Published online: 27 April 2022; doi:10.1038/s41586-022-04516-4 A study demonstrates that nitrous oxide can act as the source of O in a catalytic conversion of aryl halides to phenols, releasing N2 as by-product.

Article Description

A Hammett analysis of platinum-mediated oxy-insertion into Pt-aryl bonds is performed using DFT calculations. Modeled transformations involve the conversion of cationic Pt-aryl complexes [(bpy)Pt(R) (OY)] (R = p-X-CH; Y = 4-X-pyridine; bpy = 4,4′-X-bpy; X = NO, H, NMe) to the corresponding [(bpy)Pt(OR)] complexes via an organometallic Baeyer-Villiger (BV) pathway. Computational modeling predicts that incorporation of an electron-deficient NO group at the 4-position of pyridine-N-oxide lowers the activation barrier to the organometallic BV transformation. In contrast, computational studies reveal that increasing the donor ability of the migrating aryl group, by placement of NMe at the para position, lowers the activation barrier to the oxy-insertion step. The impact on the calculated activation barrier is greater for variation of the R group than for modification of Y of the oxygen delivery reagent. For the p-NO/p-NMe-substituted aryl migrating groups (R), the δδG for X = NMe versus X = NO is 12 kcal/mol, which is three times larger than that calculated for the changes that occur upon substitution of NO and NMe groups (δδG ≈ 4 kcal/mol) at the 4-position of the pyridine group. For these Pt complexes with bipyridine (bpy) supporting ligands, the influence of modification of the bpy ligand is calculated to be minimal with δδG ≈ 0.4 kcal/mol for the oxy-insertion of bpy ligands substituted at the 4/4′ positions with NMe and NO groups. Overall, the predicted activation barriers for oxy-insertion (from the YO adducts [( bpy)Pt(R)(OY)]) are large and in most cases are >40 kcal/mol, although some calculated δG's are as low as 32 kcal/mol. © 2011 American Chemical Society.

Bibliographic Details

Travis M. Figg; Thomas R. Cundari; T. Brent Gunnoe

American Chemical Society (ACS)

Chemistry

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