Windorff Cory J, Celis-Barros Cristian, Sperling Joseph M, McKinnon Noah C, Albrecht-Schmitt Thomas E
Department of Chemistry and Biochemistry, Florida State University 95 Chieftan Way, RM. 118 DLC Tallahassee Florida 32306 USA
Chem Sci. 2020 Feb 5;11(10):2770-2782. doi: 10.1039/c9sc05268b.
The synthesis, characterization, and theoretical analysis of meridional americium tribromide tris(tricyclohexylphosphine oxide), , has been achieved and is compared with its early lanthanide (La to Nd) analogs. The data show that homo ligands display significantly shorter bonds than the or hetero ligands. This is particularly pronounced in the americium compound. DFT along with multiconfigurational CASSCF calculations show that the contraction of the bonds relates qualitatively with overall covalency, americium shows the most covalent interactions compared to lanthanides. However, the involvement of the 5p and 6p shells in bonding follows a different order, namely cerium > neodymium ∼ americium. This study provides further insight into the mechanisms by which ITI operates in low-valent f-block complexes.
已完成对经式三溴化镅三（三环己基氧化膦）（ ）的合成、表征及理论分析，并将其与早期镧系元素（镧至钕）类似物进行了比较。数据表明，均配体显示出比 或杂配体明显更短的键。这在镅化合物中尤为明显。密度泛函理论（DFT）以及多组态完全活性空间自洽场（CASSCF）计算表明，键的收缩与整体共价性在定性上相关，与镧系元素相比，镅显示出最强的共价相互作用。然而，5p和6p壳层在成键中的参与遵循不同的顺序，即铈＞钕～镅。本研究进一步深入了解了内界相互作用（ITI）在低价态f区配合物中起作用的机制。
