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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)

Lookup NU author(s): Dr Erli Lu, Dr Stephen Liddle

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This is the authors' accepted manuscript of an article that has been published in its final definitive form by Royal Society of Chemistry, 2019.

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Abstract

© 2019 The Royal Society of Chemistry.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.


Publication metadata

Author(s): Hu S-X, Lu E, Liddle ST

Publication type: Article

Publication status: Published

Journal: Dalton Transactions

Year: 2019

Volume: 48

Issue: 34

Pages: 12867-12879

Print publication date: 14/09/2019

Online publication date: 01/08/2019

Acceptance date: 31/07/2019

Date deposited: 03/10/2019

ISSN (print): 1477-9226

ISSN (electronic): 1477-9234

Publisher: Royal Society of Chemistry

URL: https://doi.org/10.1039/C9DT03086G

DOI: 10.1039/c9dt03086g

PubMed id: 31389454


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