Prediction of High Bond-Order Metal-Metal Multiple-Bonds in Heterobimetallic 3d−4f/5f Complexes [TM-M{N(o-[NCH2P(CH3)2]C6H4)3}] (TM = Cr, Mn, Fe; M = U, Np, Pu, and Nd)

Shu-Xian Hu, Erli Lu, Stephen Liddle

Research output: Contribution to journalArticlepeer-review

Abstract

Despite continuing and burgeoning interest in f-block complexes and their bonding chemistry in recent years, investigations of the electronic structures and oxidation states of heterobimetallic complexes, and their bonding features between transition-metals (TMs) and f-elements remain relatively less explored. Here, we report a quantum chemical computational study on the series of TM-actinide and -neodymium complexes [TMAn(L)] and [TMNd(L)] [An = U, Np, Pu; TM = Cr, Mn, Fe; L = {N(o-[NCH2P(CH3)2]C6H4)3}3-] in order to explore periodic trend, generalities and differences in the electronic structure and metal–metal bonding between f-block and d-block elements. Based on the calculations, we find up to five-fold covalent multiple bonding between actinide and transition metal ions, which is in sharp contrast with a single bond between neodymium and transition metals. From a comparative study, a general trend of strength of the An-TM interaction emerges in accordance with the atomic number of the actinide metal, which relates to the nature, energy level, and spatial arrangement of their frontier orbitals. The trend presents a valuable insight for future experimental endeavour searching for isolable complexes with strong and multiple An-TM bonding interactions, especially for the experimentally challenging transuranic elements that require targeted research due to their radioactive nature.
Original languageEnglish
JournalDalton Transactions
Early online date1 Aug 2019
DOIs
Publication statusPublished - 2019

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