Wolford Nikki J, Sergentu Dumitru-Claudiu, Brennessel William W, Autschbach Jochen, Neidig Michael L
Department of Chemistry, University of Rochester, B31 Hutchison Hall, 120 Trustee Road, Rochester, NY, 14627, USA.
Department of Chemistry, University at Buffalo, State University of New York, 312 Natural Sciences Complex, Buffalo, NY, 14260, USA.
Angew Chem Int Ed Engl. 2019 Jul 22;58(30):10266-10270. doi: 10.1002/anie.201905423. Epub 2019 Jun 24.
The synthesis and characterization of sterically unencumbered homoleptic organouranium aryl complexes containing U-C σ-bonds has been of interest to the chemical community for over 70 years. Reported herein are the first structurally characterized, sterically unencumbered homoleptic uranium (IV) aryl-ate species of the form [U(Ar) ] (Ar=Ph, p-tolyl, p-Cl-Ph). Magnetic circular dichroism (MCD) spectroscopy and computational studies provide insight into electronic structure and bonding interactions in the U-C σ-bond across this series of complexes. Overall, these studies solve a decades-long challenge in synthetic uranium chemistry, enabling new insight into electronic structure and bonding in organouranium complexes.
含有U-C σ键的空间位阻较小的均配有机铀芳基配合物的合成与表征，在化学界已受到关注逾70年。本文报道了首例结构表征的、空间位阻较小的通式为[U(Ar)₄]（Ar = Ph、对甲苯基、对氯苯基）的均配铀（IV）芳基化物物种。磁圆二色性（MCD）光谱和计算研究为这一系列配合物中U-C σ键的电子结构和键合相互作用提供了深入了解。总体而言，这些研究解决了合成铀化学领域长达数十年的挑战，使人们能够对有机铀配合物的电子结构和键合有新的认识。
