Oxidation of a Dimethylplatinum(II) Complex with Oxaziridines: A Hemiaminal Intermediate but No Oxo Complex

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• 作者：Kyle R. Pellarin ; Richard J. Puddephatt
• 刊名：Organometallics
• 出版年：2013
• 出版时间：July 8, 2013
• 年：2013
• 卷：32
• 期：13
• 页码：3604-3610
• 全文大小：431K
• 年卷期：v.32,no.13(July 8, 2013)
• ISSN：1520-6041

文摘

The complex [PtMe₂(bipy)] (1; bipy = 2,2鈥?bipyridine) fails to react with the oxaziridine derivatives RCHON-t-Bu (R = H, Ph, 2-pyridyl) in acetone at room temperature, but an easy reaction occurs in methanol solution to give the platinum(IV) complex [Pt(OH)(OMe)Me₂(bipy)] and the corresponding imine RCH鈺怤-t-Bu. In the case with R = Ph, the hemiaminal intermediate [Pt(OMe)(OCHPhNH-t-Bu)Me₂(bipy)] was formed and then reacted only slowly to form [Pt(OH)(OMe)Me₂(bipy)] and PhCH鈺怤-t-Bu. Computational studies indicate that the reaction of 1 with oxaziridines occurs to give a charge transfer complex but that further reaction requires assistance from hydrogen bonding and coordination with specific methanol molecules. The work provides strong support for the theory that oxygen atom transfer to 1 from either dioxiranes or oxaziridines must be coupled to proton transfer and does not involve oxoplatinum(IV) intermediates.