Metal Bonding with 3d and 6d Orbitals: An EPR and ENDOR Spectroscopic Investigation of Ti³⁺-Al and Th³⁺-Al...

Accessing covalent bonding interactions between actinides and ligating atoms remains a central problem in the field. Our current understanding of actinide bonding is limited because of a paucity of diverse classes of compounds and the lack of established models. We recently synthesized a thorium (Th)-aluminum (Al) heterobimetallic molecule that represents a new class of low-valent Th-containing compounds. To gain further insight into this system and actinide-metal bonding more generally, it is useful to study their underlying electronic structures. Here, we report characterization by electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy of two heterobimetallic compounds: (i) a Cp^tt₂ThH₃AlCTMS₃ [TMS = Si(CH₃)₃; Cp^tt = 1,3-di- tert-butylcyclopentadienyl] complex with bridging hydrides and (ii) an actinide-free Cp₂TiH₃AlCTMS₃ (Cp = cyclopentadienyl) analogue. Analyses of the hyperfine interactions between the paramagnetic trivalent metal centers and the surrounding magnetic nuclei, ¹H and ²⁷Al, yield spin distributions over both complexes. These results show that while the bridging hydrides in the two complexes have similar hyperfine couplings ( a_iso = -9.7 and -10.7 MHz, respectively), the spin density on the Al ion in the Th³⁺ complex is ∼5-fold larger than that in the titanium(3+) (Ti³⁺) analogue. This suggests a direct orbital overlap between Th and Al, leading to a covalent interaction between Th and Al. Our quantitative investigation by a pulse EPR technique deepens our understanding of actinide bonding to main-group elements.