Electronic Structures and Properties of Bimetallic Plutonium Group 13 Carbonyl Compounds [XPuCO] (X = B, Al, and Ga)

Bonding features of heterobimetallic complexes containing f-block elements are fundamental content in actinide chemistry. In order to account for the structural periodicity of the X-Pu carbonyls and the formation of chemical bonds between bimetallic plutonium and group 13 carbonyl compounds, we report a comprehensively quantum-chemical study of the electronic structure and properties of XPuCO (X = B, Al, and Ga). With increasing atomic radii of the group 13 elements, the XPuCO structure alternates from cyclic [PuCBO] to linear [AlCPuO] and [GaCPuO]. The bonding analysis indicates that the donor-acceptor model is the best description for bonding interactions of metal and ligands with different donation patterns of CBO → Pu and XC → PuO (X = Al and Ga). The apparent XC ← PuO backdonation increases the C-Pu bond strength markedly and stabilizes the linear geometry of [AlCPuO] and [GaCPuO], while spin-orbit coupling is found to be significant in the stabilization of [PuCBO]. The ground electron configurations and natural orbital analysis indicate that cyclic [PuCBO] and linear [XCPuO] (X = Al and Ga) are considered as complexes of Pu(III) and Pu(V), respectively. The trend presents a valuable insight for the 5f/6d-np bonding interactions, especially for the fundamental understanding of transuranic elements.