Journal
ORGANOMETALLICS
Volume 36, Issue 7, Pages 1213-1216Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.7b00020
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Funding
- National Science Foundation [CHE-1464661]
- NSF Graduate Research Fellowship [DGE-1256082]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1464661] Funding Source: National Science Foundation
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The reactions of t-BuPNP and t-BuPCP Pd-II-Me complexes (t-BuPNP = 2,6-bis[(di-tert-butylphosphino)methyl]pyridine and t-BuPCP = 2,6-bis[(di-tert-butylphosphino)methyl]phenyl) with O-2 are described and compared with the reported O-2 reactivity of related Pd-II-Me complexes. [(t-BuPNP)PdMe] Cl was found to react with O-2 upon photolysis resulting in oxidation of the pincer ligand backbone to produce a (t-BuPNO)PdCl complex. In contrast, photolysis of (t-BuPCP)PdMe with O-2 resulted in oxidation of the Pd-Me group to form (t-BuPCP)PdOCO2H. Isotopic labeling, radical initiators, and solvent studies were used to gain insight into the mechanisms of these unusual reactions of late metal alkyls with molecular oxygen.
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