Insight into the nature of M-C bonding in the lanthanide/actinide-biscarbene complexes: a theoretical perspective

Dalton Transactions : an International Journal of Inorganic Chemistry
Qun-Yan WuWei-Qun Shi

Abstract

We have investigated M-C bonds in lanthanide and actinide complexes ML2 (M = Ce, Th, U, Np and Pu; L = C(PPh2NMes)2) using scalar-relativistic theory. The M-C bonds possess typical σ and π bonding character, except for the nearly π-only Th-C bonds. The metal valence electrons significantly reside in the valence d and f orbitals for CeL2, UL2, NpL2 and PuL2, while for ThL2 most electron population is in 6d orbitals. The contribution of 6d orbitals to the An-C bonds decreases and that of 5f orbitals increases across the actinide series. QTAIM (quantum theory of atoms in molecules) and NBO (natural bond orbital) analyses confirm that the M-C bonds possess significant covalent character. This work provides insights into the contributions of d and f valence orbitals to M-C bonding. And inclusion of Np and Pu in this evaluation extends understanding to later actinides.

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Citations

Jan 11, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Jie YuHaizhu Yu
Feb 9, 2019·Nature Communications·Erli LuStephen T Liddle
Nov 10, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Qun-Yan WuWei-Qun Shi
May 24, 2019·Journal of the American Chemical Society·Thibault CheissonEric J Schelter
May 24, 2019·The Journal of Physical Chemistry. a·Jian-Hui LanWei-Qun Shi
Oct 9, 2020·Inorganic Chemistry·Roger KloditzJuliane März
Jan 1, 2020·Inorganic Chemistry·Jacqueline RamlerCrispin Lichtenberg
Oct 29, 2020·ACS Omega·Attila Kovács

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Software Mentioned

EST
CPCM
Multiwfn
Gaussian
QTAIM
NBO
NOCV
ADF

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