Institut für Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum (FMF), Universität Freiburg, Albertstr. 21, 79104, Freiburg, Germany.
Karlsruhe Institute of Technology (KIT), Division Molecular Chemistry, Institute of Inorganic Chemistry, Engesserstr. 15, 76131, Karlsruhe, Germany.
Nat Commun. 2019 Feb 7;10(1):624. doi: 10.1038/s41467-019-08517-2.
Homoleptic carbonyl radical cations are a textbook family of complexes hitherto unknown in the condensed phase, leaving their properties and applications fundamentally unexplored. Here we report on two stable 17-electron [Cr(CO)] salts that were synthesized by oxidation of Cr(CO) with [NO][Al(OR)] (R = C(CF))) in CHCl and with removal of NO gas. Longer reaction times led to NO/CO ligand exchange and formation of the thermodynamically more stable 18-electron species [Cr(CO)(NO)], which belongs to the family of heteroleptic chromium carbonyl/nitrosyl cations. All salts were fully characterized (IR, Raman, EPR, NMR, scXRD, pXRD, magnetics) and are stable at room temperature under inert conditions over months. The facile synthesis of these species enables the thorough investigation of their properties and applications to a broad scientific community.
同核羰基自由基阳离子是一类教科书中典型的配合物，迄今在凝聚相中尚未被发现，其性质和应用仍未得到深入研究。在这里，我们报告了两种稳定的 17 电子[Cr(CO)]盐，它们是通过在 CHCl 中用[NO][Al(OR)]（R = C(CF3))氧化 Cr(CO)并除去 NO 气体合成的。更长的反应时间会导致 NO/CO 配体交换，并形成热力学上更稳定的 18 电子物种[Cr(CO)(NO)]，它属于杂核铬羰基/亚硝酰阳离子家族。所有盐都经过了充分的表征（IR、Raman、EPR、NMR、scXRD、pXRD、磁性），在惰性条件下在室温下稳定数月。这些物质的简便合成使它们的性质和应用能够被广泛的科学界进行深入研究。
