A Very Short Uranium(IV)–Rhodium(I) Bond with Net Double‐Dative Bonding Character |
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| Authors: | Dr. Erli Lu Dr. Ashley J. Wooles Dr. Matthew Gregson Philip J. Cobb Prof. Stephen T. Liddle |
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| Affiliation: | School of Chemistry, The University of Manchester, Manchester, UK |
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| Abstract: | 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?RhI2 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 UIV net double dative bond interaction, involving RhI 4d ‐ 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. |
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| Keywords: | carbenes C− H activation metal– metal bonding rhodium uranium |
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