Radicalizing CO by Mononuclear Palladium(I)
Tim Bruckhoff, Joachim Ballmann, Lutz H. Gade
Abstract
metalloradical (3), stabilized by a bulky carbazole-based PNP-ligand, was obtained by reduction of palladium chloride or thermal Pd-C bond homolysis of the corresponding neopentyl complex. Pressurizing with CO gave the Pd(I) carbonyl complex, which was structurally characterized by X-ray diffraction. Delocalization of the unpaired electron to the carbonyl carbon was detected by EPR spectroscopy and theoretically modeled by DFT and ab initio methods. The partially reduced and radicalized CO slowly reacts with di(tert-butyl) disulfide under homolytic S-S cleavage and C-S bond formation to give the corresponding metallathioester.
Topics & Concepts
HomolysisPalladiumChemistryUnpaired electronElectron paramagnetic resonanceDelocalized electronLigand (biochemistry)Bond cleavagePhotochemistryAb initioMedicinal chemistryCrystallographyStereochemistryCatalysisOrganic chemistryRadicalNuclear magnetic resonanceReceptorPhysicsBiochemistryOrganometallic Complex Synthesis and CatalysisCO2 Reduction Techniques and CatalystsCarbon dioxide utilization in catalysis