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A Very Short Uranium(IV)–Rhodium(I) Bond with Net Double-Dative Bonding Character

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

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This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).

Abstract

© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Reaction of [U{C(SiMe3)(PPh2)}(BIPM)(μ-Cl)Li(TMEDA)(μ-TMEDA)0.5]2 (BIPM=C(PPh2NSiMe3)2; TMEDA=Me2NCH2CH2NMe2) with [Rh(μ-Cl)(COD)]2 (COD=cyclooctadiene) affords the heterotrimetallic UIV−RhI 2 complex [U(Cl)2{C(PPh2NSiMe3)(PPh[C6H4]NSiMe3)}{Rh(COD)}{Rh(CH(SiMe3)(PPh2)}]. This complex has a very short uranium–rhodium distance, the shortest uranium–rhodium bond on record and the shortest actinide–transition metal bond in terms of formal shortness ratio. Quantum-chemical calculations reveal a remarkable Rh (Formula presented.) UIV net double dative bond interaction, involving RhI 4d Z2 - and 4dxy/xz-type donation into vacant UIV 5f orbitals, resulting in a Wiberg/Nalewajski–Mrozek U−Rh bond order of 1.30/1.44, respectively. Despite being, formally, purely dative, the uranium–rhodium bonding interaction is the most substantial actinide–metal multiple bond yet prepared under conventional experimental conditions, as confirmed by structural, magnetic, and computational analyses.

Publication metadata

Author(s): Lu E, Wooles AJ, Gregson M, Cobb PJ, Liddle ST

Publication type: Article

Publication status: Published

Journal: Angewandte Chemie International Edition

Year: 2018

Volume: 57

Issue: 22

Pages: 6587-6591

Print publication date: 28/05/2018

Online publication date: 17/04/2018

Acceptance date: 17/04/2018

Date deposited: 02/10/2019

ISSN (print): 1433-7851

ISSN (electronic): 1521-3773

Publisher: Wiley - VCH Verlag

URL: https://doi.org/10.1002/anie.201803493

DOI: 10.1002/anie.201803493

PubMed id: 29665209

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