Lu Erli, Wooles Ashley J, Gregson Matthew, Cobb Philip J, Liddle Stephen T
School of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
Angew Chem Int Ed Engl. 2018 May 28;57(22):6587-6591. doi: 10.1002/anie.201803493. Epub 2018 Apr 27.
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.
[U{C(SiMe₃)(PPh₂)}(BIPM)(μ-Cl)Li(TMEDA)(μ-TMEDA)]（BIPM = C(PPh₂NSiMe₃)₂；TMEDA = Me₂NCH₂CH₂NMe₂）与[Rh(μ-Cl)(COD)]（COD = 环辛二烯）反应生成异三金属U-Rh配合物[U(Cl)₂{C(PPh₂NSiMe₃)(PPh[C₆H₄]NSiMe₃)}{Rh(COD)}{Rh(CH(SiMe₃)(PPh₂)}]。该配合物具有非常短的铀-铑距离，是有记录以来最短的铀-铑键，并且就形式短程比而言是最短的锕系元素-过渡金属键。量子化学计算揭示了一种显著的RhI→→U净双配位键相互作用，涉及Rh 4dz²和4d轨道向U的空5f轨道的电子给予，导致Wiberg/Nalewajski-Mrozek铀-铑键级分别为1.30/1.44。尽管从形式上看纯粹是配位键，但铀-铑键相互作用是在常规实验条件下制备的最显著的锕系元素-金属多重键，结构、磁性和计算分析均证实了这一点。
