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
- 36Citations
- 14Captures
- 1Mentions
Metric Options: Counts1 Year3 YearSelecting the 1-year or 3-year option will change the metrics count to percentiles, illustrating how an article or review compares to other articles or reviews within the selected time period in the same journal. Selecting the 1-year option compares the metrics against other articles/reviews that were also published in the same calendar year. Selecting the 3-year option compares the metrics against other articles/reviews that were also published in the same calendar year plus the two years prior.
Example: if you select the 1-year option for an article published in 2019 and a metric category shows 90%, that means that the article or review is performing better than 90% of the other articles/reviews published in that journal in 2019. If you select the 3-year option for the same article published in 2019 and the metric category shows 90%, that means that the article or review is performing better than 90% of the other articles/reviews published in that journal in 2019, 2018 and 2017.
Citation Benchmarking is provided by Scopus and SciVal and is different from the metrics context provided by PlumX Metrics.
Example: if you select the 1-year option for an article published in 2019 and a metric category shows 90%, that means that the article or review is performing better than 90% of the other articles/reviews published in that journal in 2019. If you select the 3-year option for the same article published in 2019 and the metric category shows 90%, that means that the article or review is performing better than 90% of the other articles/reviews published in that journal in 2019, 2018 and 2017.
Citation Benchmarking is provided by Scopus and SciVal and is different from the metrics context provided by PlumX Metrics.
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
Provide Feedback
Have ideas for a new metric? Would you like to see something else here?Let us know