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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



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

For re-use rights please refer to the publisher's terms and conditions.


© 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


DOI: 10.1039/c9dt03086g

PubMed id: 31389454


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