Tin(II)–Nitrene Radical Complexes Formed by Electron Transfer from Redox-Active Ligand to Organic Azides and Their Reactivity in C(sp<sup>3</sup>)–H Activation
Hideki Sugimoto, Mayuka Yano, Kazunobu Sato, Mayuko Miyanishi, Kenji Sugisaki, Yoshihito Shiota, Akira Kaga, Kazunari Yoshizawa, Shinobu Itoh
Abstract
A tin(II) complex coordinated by a sterically demanding o-phenylenediamido ligand is synthesized. The ligand is redox-active to reach a tin(II) complex with the diiminobenzosemiquinone radial anion in the oxidation by AgPF6. The tin(II) complex reacts with a series of nosylazides (x-NO2C6H4–SO2–N3; x = o, m, or p) at −30 °C to yield the corresponding nitrene radical bound tin(II) complexes. The nitrene radical complexes exhibit C(sp3)–H activation and amination reactivity.
Topics & Concepts
NitreneChemistryTinReactivity (psychology)Ligand (biochemistry)RedoxPhotochemistrySteric effectsElectron transferMedicinal chemistryAminationStereochemistryInorganic chemistryOrganic chemistryCatalysisReceptorPathologyMedicineAlternative medicineBiochemistrySynthesis and Catalytic ReactionsCatalytic C–H Functionalization MethodsMetal-Catalyzed Oxygenation Mechanisms