AEROBIC OXIDATION OF CIS-2-BUTENE AND 2-BUTYNE IN WATER MEDIATED BY (DPMS)PtII (DPMS = DI(2-PYRIDYL) METHANE SULFONATE)
Abstract
(dpms)Pt<super>II</super> hydroxo ethylene complex <bold>(2.1)</bold> undergoes ligand substitution--intramolecular hydroxo platination with 2-butyne in water to give Pt<super>II</super> η<super>1<super/>-ketonyl complex <bold>(2.2)</bold>. This neutral complex is oxidized by O<sub>2</sub> or H<sub>2</sub>O<sub>2</sub> to give Pt<super>IV</super> secondary alkyl complex <bold>(2.4)</bold>. Oxidation by O<sub>2</sub> was found to be pH dependent. Also described here is the preparation of Pt<super>IV</super> oxetane <bold>(3.2)</bold> derived from non-cyclic non-strained olefin, <italic>cis</italic>-2-butene. The starting complex here is the (dpms)Pt<super>II</super> chloro <italic>cis</italic>-2-butene <bold>(3.1)</bold> which undergoes chloride abstraction by Ag<sub>2</sub>O to give the hydroxo analog before getting oxidized by O<sub>2<1sub> to Pt<super>IV</super> oxetane.