Anderton Kevin J, Knight Brian J, Rheingold Arnold L, Abboud Khalil A, García-Serres Ricardo, Murray Leslie J
Center for Catalysis , University of Florida , 214 Leigh Hall P.O. Box 117200 , Gainesville , FL 32611 , USA . Email:
Department of Chemistry and Biochemistry , University of California San Diego , 9500 Gilman Drive, MC 0358 , La Jolla , CA 92093-0358 , USA.
Chem Sci. 2017 May 1;8(5):4123-4129. doi: 10.1039/c6sc05583d. Epub 2017 Apr 11.
The triiron trihydride complex FeH () [where is a tris(β-diketiminate)cyclophanate] reacts with CO and with BF·OEt to afford (FeCO)Fe(μ-H) () and FeF (), respectively. Variable-temperature and applied-field Mössbauer spectroscopy support the assignment of two high-spin (HS) iron(i) centers and one HS iron(ii) ion in . Preliminary studies support a CO-induced reductive elimination of H from , rather than CO trapping a species from an equilibrium mixture. This complex reacts with H to regenerate under a dihydrogen atmosphere, which represents a rare example of reversible CO/H exchange and the first to occur at high-spin metal centers, as well as the first example of a reversible multielectron redox reaction at a designed high-spin metal cluster. The formation of proceeds through a previously unreported net fluoride-for-hydride substitution, and is surprisingly chemically inert to Si-H bonds and points to an unexpectedly large difference between the Fe-F and Fe-H bonds in this high-spin system.
三氢化三铁配合物FeH（其中 是三（β - 二酮亚胺）环戊二烯酸盐）与CO和BF·OEt反应，分别生成(FeCO)Fe(μ - H)（）和FeF（）。变温和外加磁场穆斯堡尔光谱支持在 中存在两个高自旋（HS）铁（I）中心和一个HS铁（II）离子的归属。初步研究支持CO诱导从 中还原消除H，而不是CO从平衡混合物中捕获一种物质。该配合物在氢气气氛下与H反应再生 ，这代表了可逆CO/H交换的罕见例子，也是首次在高自旋金属中心发生的例子，以及在设计的高自旋金属簇上首次发生的可逆多电子氧化还原反应的例子。 的形成通过先前未报道的净氟代氢取代进行，并且 对Si - H键具有惊人的化学惰性，这表明在这个高自旋体系中Fe - F键和Fe - H键之间存在意想不到的巨大差异。
