Reactivity Control in Iron(III) Amino Triphenolate Complexes: Comparison of Monomeric and Dimeric Complexes
作者:Christopher J. Whiteoak、Blerina Gjoka、Eddy Martin、Marta Martínez Belmonte、Eduardo C. Escudero-Adán、Cristiano Zonta、Giulia Licini、Arjan. W. Kleij
DOI:10.1021/ic3008624
日期:2012.10.15
These analytical studies have shown that the monomeric and dimeric [FeLR] complexes behave distinctively, and that the dimer stability is a function of the ortho-positioned groups. Both the dimeric as well as monomeric complexes were tested as catalysts for the catalytic cycloaddition of carbon dioxide to oxiranes, and the data show that the monomeric complexes are able to mediate this conversion with
铁(III)氨基triphenolate配合物在不同的取代基邻位的酚盐部分(R = H,Me中的位置吨Bu或PH)已经由铁(III),氯化和钠盐的反应合成(钠3 L R)的必要配体。通过X射线衍射,1 H NMR,溶液磁化率和循环伏安法研究相结合,已证明该络合物具有单体([FeL R(THF)])或二聚体([FeL R ] 2)性质。。这些分析研究表明,单体和二聚体[FeL R配合物表现出明显的不同,并且二聚体稳定性是邻位基团的函数。测试了二聚体和单体配合物两者作为二氧化碳催化环加成到环氧乙烷的催化剂,并且数据表明,与二聚体配合物相比,单体配合物能够以显着更高的活性介导这种转化。在反应性的这种差异是通过在配位体L的取代模式控制- [R ,并且与由铁(III)中心环氧化物底物结合的催化所需的线路。