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A Very Short Uranium(IV)–Rhodium(I) Bond with Net Double‐Dative Bonding Character
Author(s) -
Lu Erli,
Wooles Ashley J.,
Gregson Matthew,
Cobb Philip J.,
Liddle Stephen T.
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201803493
Subject(s) - rhodium , chemistry , actinide , uranium , double bond , metal , crystallography , stereochemistry , catalysis , inorganic chemistry , organic chemistry , materials science , metallurgy
Reaction of [U{C(SiMe 3 )(PPh 2 )}(BIPM)(μ‐Cl)Li(TMEDA)(μ‐TMEDA) 0.5 ] 2 (BIPM=C(PPh 2 NSiMe 3 ) 2 ; TMEDA=Me 2 NCH 2 CH 2 NMe 2 ) with [Rh(μ‐Cl)(COD)] 2 (COD=cyclooctadiene) affords the heterotrimetallic U IV −Rh I 2 complex [U(Cl) 2 {C(PPh 2 NSiMe 3 )(PPh[C 6 H 4 ]NSiMe 3 )}{Rh(COD)}{Rh(CH(SiMe 3 )(PPh 2 )}]. 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 RhI→→U IV net double dative bond interaction, involving Rh I 4dz2‐ and 4d xy/xz ‐type donation into vacant U IV 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.