钼和锑卟吩的合成、全面表征以及后一种配合物作为高效催化剂用于高选择性好氧氧化反应的应用。

Synthesis and full characterization of molybdenum and antimony corroles and utilization of the latter complexes as very efficient catalysts for highly selective aerobic oxygenation reactions.

作者信息

Luobeznova Inna, Raizman Marina, Goldberg Israel, Gross Zeev

机构信息

Department of Chemistry and Institute of Catalysis Science and Technology, Technion-Israel Institute of Technology, Haifa.

出版信息

Inorg Chem. 2006 Jan 9;45(1):386-94. doi: 10.1021/ic051483g.

DOI:10.1021/ic051483g

PMID:16390079

Abstract

Two molybdenum and three antimony corroles were isolated and characterized by NMR, EPR, and electrochemistry. The very negative reduction potentials of the (oxo)molybdenum(V) corroles are clearly related to their inactivity as oxygen transfer reagents and the unsuccessful attempts to isolate lower-valent molybdenum corroles. X-ray crystallography of the (oxo)molybdenum(V) corrole 1a and the trans-difluoroantimony(V) corrole 2c, the first of their kind, revealed that their molecular structures represent extreme cases of such complexes: a highly domed corrole with very large out-of-plane metal displacement for 1a (0.73 Angstroms) and a very flat corrole with the metal ion in its center for 2c. All three antimony corroles displayed high activity and selectivity as catalysts for the photoinduced oxidation of thioanisole by molecular oxygen, with superior results obtained in alcoholic solvents with 2c as catalyst. Allylic and tertiary benzylic CH bonds were also oxidized under those conditions, with absolute selectivity to the corresponding hydroperoxides.

摘要

分离出了两种钼和三种锑的卟吩，并通过核磁共振（NMR）、电子顺磁共振（EPR）和电化学方法对其进行了表征。（氧代）钼（V）卟吩非常负的还原电位显然与其作为氧转移试剂的不活性以及分离低价钼卟吩的尝试失败有关。首例（氧代）钼（V）卟吩1a和反式二氟锑（V）卟吩2c的X射线晶体学研究表明，它们的分子结构代表了这类配合物的极端情况：对于1a，是一个高度圆顶状的卟吩，金属的平面外位移非常大（0.73埃）；对于2c，是一个非常扁平的卟吩，金属离子位于其中心。所有三种锑卟吩作为分子氧光诱导氧化苯甲硫醚的催化剂均表现出高活性和选择性，以2c为催化剂在醇类溶剂中获得了更好的结果。在这些条件下，烯丙基和叔苄基的碳氢键也被氧化，对相应的氢过氧化物具有绝对选择性。