Reaction of [U{C(SiMe )(PPh )}(BIPM)(μ-Cl)Li(TMEDA)(μ-TMEDA) ] (BIPM=C(PPh NSiMe ) ; TMEDA=Me NCH CH NMe ) with [Rh(μ-Cl)(COD)] (COD=cyclooctadiene) affords the heterotrimetallic U -Rh complex [U(Cl) {C(PPh NSiMe )(PPh[C H ]NSiMe )}{Rh(COD)}{Rh(CH(SiMe )(PPh )}]. 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 net double dative bond interaction, involving Rh 4dz2 - and 4d -type donation into vacant U 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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| http://dx.doi.org/10.1002/anie.201803493 | DOI Listing |
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