Alkene Oxidation by a Platinum Oxo Complex and Isolation of a Platinaoxetane
摘要:
Oxo complex [(1,5-COD)4Pt4(mu3-O)2Cl2](BF4)2 (1) reacts readily with ethylene and norbornylene. The ethylene reaction yields acetaldehyde and a 1:1 mixture of (1,5-COD)Pt(Cl)(CH2CH3) (2) and [(1,5-COD)Pt4(eta3-CH2CHCH(CH3))](BF4) (3), while the norbornylene reaction yields a platinaoxetane complex, the first metallaoxetane to be obtained from the reaction of an oxo complex and an alkene.
Reversible alkene extrusion from platinaoxetanes has been observed. Catalytic amounts of electrophilic Pt complexes, HOTf, Ag+, or BF3 (best) result in dramatic rate enhancements.
作者:Nandita M. Weliange、Endre Szuromi、Paul R. Sharp
DOI:10.1021/ja902180k
日期:2009.7.1
Formation of 2-platinaoxetane 2 from oxo complex 1 and norbornene (NB) is mediated by hydroxo complex 5. The facile reaction of 5 with NB to give protonated 2-platinaoxetane 7 supports the involvement of such reactions in Wacker alkene oxidation.