Formanuik Alasdair, Ortu Fabrizio, Liu Jingjing, Nodaraki Lydia E, Tuna Floriana, Kerridge Andrew, Mills David P
School of Chemistry, The University of Manchester, Manchester, M13 9PL, UK.
Department of Chemistry, Lancaster University, Lancaster, LA1 4YB, UK.
Chemistry. 2017 Feb 16;23(10):2290-2293. doi: 10.1002/chem.201605974. Epub 2017 Jan 25.
The redox chemistry of uranium is burgeoning and uranium(III) complexes have been shown to promote many interesting synthetic transformations. However, their utility is limited by their reduction potentials, which are smaller than many non-traditional lanthanide(II) complexes. Thorium(III) has a greater redox potential so it should present unprecedented opportunities for actinide reactivity but as with uranium(II) and thorium(II) chemistry, these have not yet been fully realized. Herein we present reactivity studies of two equivalents of [Th(Cp'') ] (1, Cp''={C H (SiMe ) -1,3}) with 4,4'-bipyridine or two equivalents of pyridine to give [{Th(Cp'') } {μ-(NC H ) }] (2) and [{Th(Cp'') } {μ-(NC H ) }] (3), respectively. As relatively large reduction potentials are required to effect these transformations we have shown that thorium(III) can promote reactions that uranium(III) cannot, opening up promising new reductive chemistry for the actinides.
铀的氧化还原化学正在蓬勃发展，并且已表明铀(III)配合物能促进许多有趣的合成转化反应。然而，它们的效用受到其还原电位的限制，该还原电位比许多非传统的镧系元素(II)配合物的还原电位小。钍(III)具有更大的氧化还原电位，因此它应该为锕系元素的反应性提供前所未有的机会，但与铀(II)和钍(II)化学一样，这些机会尚未得到充分实现。在此，我们展示了两当量的[Th(Cp'') ] (1，Cp'' = {C H (SiMe ) -1,3})与4,4'-联吡啶或两当量吡啶反应，分别生成[{Th(Cp'') } {μ-(NC H ) }] (2)和[{Th(Cp'') } {μ-(NC H ) }] (3)的反应研究。由于实现这些转化需要相对较大的还原电位，我们已表明钍(III)能够促进铀(III)无法促进的反应，为锕系元素开辟了有前景的新还原化学。
