When Applying the Mercury Poisoning Test to Palladacycle-Catalyzed Reactions, One Should Not Consider the Common Misconception of Mercury(0) Selectivity

• Published in: Organometallics Vol. 37; no. 17; pp. 2842 - 2858
• Main Authors: Gorunova, Olga N, Novitskiy, Ivan M, Grishin, Yuri K, Gloriozov, Igor P, Roznyatovsky, Vitaly A, Khrustalev, Victor N, Kochetkov, Konstantin A, Dunina, Valery V
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 10.09.2018; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Physical Sciences; Science & Technology; ORGANOMETALLIC COMPOUNDS; MOLECULAR-STRUCTURE; PINCER COMPLEXES; ORGANOMERCURY COMPOUNDS; CRYSTAL-STRUCTURES; HETEROGENEOUS CATALYSIS; DER-WAALS RADII; MIZOROKI-HECK; SUZUKI-MIYAURA; TRANSMETALATION REACTIONS
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/acs.organomet.8b00363

The aim of this study was to demonstrate the absolute necessity of control experiments for a correct interpretation of mercury drop test results when applied to mechanistic studies of palladacycle-catalyzed reactions. It was shown that the interaction of diverse azapalladacycles with metallic mercury leads to the formation of organomercuric chlorides during the redox-transmetalation process. The structure of these organomercurials was confirmed by elemental analysis, 1H, 13C­{1H}, and 199Hg­{1H} NMR spectra, X-ray diffraction analysis, and DFT calculations. The behavior and properties of C,N-mercuracycles bearing the weak and labile N···Hg bond are discussed on the basis of the temperature dependence of the NMR spectra and calculated thermodynamic parameters of the dechelation process.