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

Reaction of [U{C(SiMe3 )(PPh2 )}(BIPM)(μ-Cl)Li(TMEDA)(μ-TMEDA)0.5 ]2 (BIPM=C(PPh2 NSiMe3 )2 ; TMEDA=Me2 NCH2 CH2 NMe2 ) with [Rh(μ-Cl)(COD)]2 (COD=cyclooctadiene) affords the heterotrimetallic UIV -RhI2 complex [U(Cl)2 {C(PPh2 NSiMe3 )(PPh[C6 H4 ]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 RhI→→ UIV net double dative bond interaction, involving RhI 4dz2 - 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.