Insertion of Molecular Oxygen into Palladium and Platinum-sp<sup>3</sup> Carbon Bonds
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- Ura Yasuyuki
- Department of Chemistry, Faculty of Science, Nara Womenʼs University
Bibliographic Information
- Other Title
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- パラジウムおよび白金－ sp<sup>3</sup> 炭素結合への分子状酸素の挿入反応
- パラジウムおよび白金-sp³炭素結合への分子状酸素の挿入反応
- パラジウム オヨビ ハッキン-sp ³ タンソ ケツゴウ エ ノ ブンシジョウ サンソ ノ ソウニュウ ハンノウ
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Abstract
Synthesis of methanol from methane and terminal alcohols from linear alkanes using molecular oxygen as an oxidant under mild conditions is an attractive and environmentally-friendly transformation reaction. Insertion of molecular oxygen into a transition metal-carbon (sp3) bond is a key step to achieve the transition metal complex-catalyzed transformation. In this review, two mechanistically-different insertion reactions of oxygen into palladium and platinum-carbon (sp3) bonds are introduced. The former insertion is proposed to proceed by a radical chain mechanism, which is similar to that for the auto oxidation of organic compounds. A palladium(III) 17e- intermediate, [PdIIIMe2(OOMe)(bipy)] (bipy = 2,2'-bipyridine), which would be formed by the attack of a methylperoxy radical to [PdMe2(bipy)], is regarded as a characteristic species in the proposed mechanism. On the other hand, the latter insertion involves loosely aggregated Pd(II) or Pt(II) methyl complexes, [Me(L)MII…MII(L)Me] (L = 6,6''-diamino-2,2':6',2''-terpyridine), which would be excited to triplet complexes, 3[Me(L)MIII–MIII(L)Me]*, upon exposure to light. Subsequent coordination of triplet oxygen and further conversions including reductive elimination of a carbon (sp3)- oxygen bond at the final step afford [MII(L)OOMe].
Journal
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- Bulletin of Japan Society of Coordination Chemistry
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Bulletin of Japan Society of Coordination Chemistry 65 (0), 49-52, 2015
Japan Society of Coordination Chemistry