The contribution of ligand flexibility to metal center geometry modulated thermal cyclization of conjugated pyridine and quinoline metalloenediynes of copper(I) and copper(II)

Inorganic Chemistry
D S RawatJ M Zaleski

Abstract

We report the syntheses, reactivities, and structure evaluations of a series of Cu(I) and Cu(II) metalloenediynes of conjugated 1,6-bis(pyridine-3)hex-3-ene-1,5-diyne (PyED, 7) and 1,6-bis(quinoline-3)hex-3-ene-1,5-diyne (QnED, 8) enediyne ligands, as well as their benzoenediyne analogues. Differential scanning calorimetry demonstrates that the [Cu(PyED)(2)](NO(3))(2) (11) exhibits a Bergman cyclization temperature (156 degrees C) which is dramatically reduced from that of the corresponding [Cu(PyED)(2)](PF(6)) (19) analogue (326 degrees C), indicating that large differences in the reactivities of these metalloenediynes can be accessed by variations in metal oxidation state. The distorted, 4-coordinate dichloride compound Cu(PyED)(Cl)(2) (15) exhibits a cyclization temperature (265 degrees C) between those of 11 and 19, suggesting that variation in geometry of the copper center is responsible for the wide range of reactivities. Similar results are obtained for the benzoenediyne and quinoline analogues. The structures of the Cu(II) systems have also been evaluated by a combination of electronic absorption and EPR spectroscopies which reveal tetragonal, 6-coordinate structures for the bis(enediyne) complexes, and tetrahedrally di...Continue Reading

References

Oct 30, 1992·Biochemical and Biophysical Research Communications·T ShirakiY Sugiura
May 1, 1990·Proceedings of the National Academy of Sciences of the United States of America·Y SugiuraT Oki
Sep 15, 1993·Biochemical and Biophysical Research Communications·T MatsumotoY Sugiura

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Citations

Oct 18, 2011·Medicinal Chemistry Research : an International Journal for Rapid Communications on Design and Mechanisms of Action of Biologically Active Agents·Stanisław BoryczkaEwa Bębenek
Jan 2, 2010·Journal of the American Society for Mass Spectrometry·Yi ChenQian Wang
May 22, 2002·Biochimica Et Biophysica Acta·Malcolm A LyonsAndrew J Brown
Oct 26, 2005·Chemical Communications : Chem Comm·Sibaprasad BhattacharyyaJeffrey M Zaleski
Mar 17, 2012·Chemistry & Biodiversity·Mukesh C Joshi, Diwan S Rawat
Feb 26, 2013·Journal of the American Chemical Society·Sarah E LindahlJeffrey M Zaleski
May 16, 2018·Radiation Research·Eric J KellerJoseph R Dynlacht
Oct 9, 2003·Chemical Reviews·Amit BasakSubhendu Sekhar Bag
Jan 21, 2004·Inorganic Chemistry·Tilak ChandraJeffrey M Zaleski
Apr 21, 2005·Journal of the American Chemical Society·Matthew T Stone, Jeffrey S Moore
Apr 16, 2002·Inorganic Chemistry·Yi-Zhen HuRandolph P Thummel
Nov 26, 2010·Inorganic Chemistry·Brigitte R SpencerJeffrey M Zaleski
Mar 17, 2004·Inorganic Chemistry·Parbati SenguptaDavid Y Son
Sep 27, 2001·Journal of the American Chemical Society·D S Rawat, J M Zaleski

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