Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, United States.
J Am Chem Soc. 2015 May 20;137(19):6366-72. doi: 10.1021/jacs.5b02504. Epub 2015 May 6.
The synthesis of the first heteroleptic, two-coordinate Fe(I) complex IPr-Fe-N(SiMe3)DIPP (1) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; DIPP = 2,6-(i)Pr2-C6H3) is reported. Protonation of the Fe(II) bis(amido) complex Fe[N(SiMe3)DIPP]2 followed by addition of IPr and reduction by potassium graphite in a one-pot reaction results in good yields of 1. The redox activity of 1 and comparison between 1 and its reduction product by (57)Fe Mössbauer spectroscopy are discussed, and the reduction was found to be metal-based rather than ligand-based. The activity of 1 toward the catalytic cyclotrimerization of terminal and internal alkynes is described.
本文报道了首例异双核、二配位 Fe(I) 配合物 IPr-Fe-N(SiMe3)DIPP（1）（IPr = 1,3-双（2,6-二异丙基苯基）咪唑-2-亚基；DIPP = 2,6-（i）Pr2-C6H3）的合成。通过一锅反应，Fe(II)双（酰胺）配合物 Fe[N(SiMe3)DIPP]2 质子化后，加入 IPr 并还原为钾石墨，得到了 1 的良好产率。讨论了 1 的氧化还原活性以及 1 与其通过 (57)Fe Mössbauer 光谱还原产物的比较，并发现还原是基于金属而不是配体的。还描述了 1 对末端和内部炔烃的催化环三聚反应的活性。
