Bis-triazinyl pyridines (BTPs) exhibit solution selectivity for trivalent americium over lanthanides (Ln), the origins of which remain uncertain. Here, electrospray ionization was used to generate gas-phase complexes [ML₃]³⁺, where M = La, Lu, or Am and L is EtBTP 2,6-bis(5,6-diethyl-1,2,4-triazin-3-yl)-pyridine. Collision-induced dissociation (CID) of [ML₃]³⁺ in the presence of H₂O yielded a protonated ligand [L(H)]⁺ and hydroxide [ML₂(OH)]²⁺ or hydrate [ML(L-H)(H₂O)]²⁺, where (L-H)^- is a deprotonated ligand. Although solution affinities indicate stronger binding of BTPs toward Am³⁺ versus Ln³⁺, the observed CID process is contrastingly more facile for M = Am versus Ln. To understand the disparity, density functional theory was employed to compute potential energy surfaces for two possible CID processes, for M = La and Am. In accordance with the CID results, both the rate determining transition state barrier and the net energy are lower for [AmL₃]³⁺ versus [LaL₃]³⁺ and for both product isomers, [ML₂(OH)]²⁺ and [ML(L-H)(H₂O)]²⁺. More facile removal of a ligand from [AmL₃]³⁺ by CID does not necessarily contradict stronger Am³⁺-L binding, as inferred from solution behavior. In particular, the formation of new bonds in the products can distort kinetics and thermodynamics expected for simple bond cleavage reactions. In addition to correctly predicting the seemingly anomalous CID behavior, the computational results indicate greater participation of Am 5f versus La 4f orbitals in metal-ligand bonding.

Reaction of the thorium metallacycle, [Th{N(R)(SiMe₂)CH₂}(NR₂)₂] (R = SiMe₃) with 1 equiv. of NaNH₂ in THF, in the presence of 18-crown-6, results in formation of the bridged thorium nitride complex, [Na(18-crown-6)(Et₂O)][(R₂N)₃Th(μ-N)(Th(NR₂)₃] ([Na][1]), which can be isolated in 66% yield after work-up. Complex [Na][1] is the first isolable molecular thorium nitride complex. Mechanistic studies suggest that the first step of the reaction is deprotonation of [Th{N(R)(SiMe₂)CH₂}(NR₂)₂] by NaNH₂, which results in formation of the thorium bis(metallacycle) complex, [Na(THF) _x ][Th{N(R)(SiMe₂CH₂)}₂(NR₂)], and NH₃. NH₃ then reacts with unreacted [Th{N(R)(SiMe₂)CH₂}(NR₂)₂], forming [Th(NR₂)₃(NH₂)] (2), which protonates [Na(THF) _x ][Th{N(R)(SiMe₂CH₂)}₂(NR₂)] to give [Na][1]. Consistent with hypothesis, addition of excess NH₃ to a THF solution of [Th{N(R)(SiMe₂)CH₂}(NR₂)₂] results in formation of [Th(NR₂)₃(NH₂)] (2), which can be isolated in 51% yield after work-up. Furthermore, reaction of [K(DME)][Th{N(R)(SiMe₂CH₂)}₂(NR₂)] with 2, in THF-d ₈, results in clean formation of [K][1], according to ¹H NMR spectroscopy. The electronic structures of [1]^- and 2 were investigated by ¹⁵N NMR spectroscopy and DFT calculations. This analysis reveals that the Th-N_nitride bond in [1]^- features more covalency and a greater degree of bond multiplicity than the Th-NH₂ bond in 2. Similarly, our analysis indicates a greater degree of covalency in [1]^- vs. comparable thorium imido and oxo complexes.

Reaction of [Ce(NO₃)₃(THF)₄] with 6 equiv of Li(N═C^tBuPh), followed by addition of 0.5 equiv of I₂, affords the homoleptic Ce(IV) ketimide [Li]₂[Ce(N═C^tBuPh)₆] (1), which can be isolated in 44% yield after workup. Similarly, reaction of [ThCl₄(DME)₂] (DME = 1,2-dimethoxyethane) with 6 equiv of Li(N═C^tBuPh) in tetrahydrofuran affords the isostructural Th(IV) ketimide [Li]₂[Th(N═C^tBuPh)₆] (2), which can be isolated in 53% yield after workup. Both 1 and 2 were fully characterized, including analysis by X-ray crystallography, allowing for a detailed structural and spectroscopic comparison. The electronic structures of 1 and 2 were also explored with density functional theory and multiconfigurational wave function calculations. Additionally, the redox chemistry of 1 was probed by cyclic voltammetry, which revealed a highly cathodic Ce(IV)/Ce(III) reduction potential, providing evidence for the ability of the ketimide ligand to stabilize high oxidation states of the lanthanides.

Core-resonant circular dichroism (CD) signals are induced by molecular chirality and vanish for achiral molecules and racemic mixtures. The highly localized nature of core excitations makes them ideal probes of local chirality within molecules. Simulations of the circular dichroism spectra of several molecular families illustrate how these signals vary with the electronic coupling to substitution groups, the distance between the X-ray chromophore and the chiral center, geometry, and chemical structure. Clear insight into the molecular structure is obtained through analysis of the X-ray CD spectra.

The reaction of [AnCl(NR₂)₃] (An = U, Th, R = SiMe₃) with in situ generated lithium-3,3-diphenylcyclopropene results in the formation of [{(NR₂)₃}An(CH[double bond, length as m-dash]C[double bond, length as m-dash]CPh₂)] (An = U, 1; Th, 2) in good yields after work-up. Deprotonation of 1 or 2 with LDA/2.2.2-cryptand results in formation of the anionic allenylidenes, [Li(2.2.2-cryptand)][{(NR₂)₃}An(CCCPh₂)] (An = U, 3; Th, 4). The calculated ¹³C NMR chemical shifts of the C_α, C_β, and C_γ nuclei in 2 and 4 nicely reproduce the experimentally assigned order, and exhibit a characteristic spin-orbit induced downfield shift at C_α due to involvement of the 5f orbitals in the Th-C bonds. Additionally, the bonding analyses for 3 and 4 show a delocalized multi-center character of the ligand π orbitals involving the actinide. While a single-triple-single-bond resonance structure (e.g., An-C[triple bond, length as m-dash]C-CPh₂) predominates, the An[double bond, length as m-dash]C[double bond, length as m-dash]C[double bond, length as m-dash]CPh₂ resonance form contributes, as well, more so for 3 than for 4.

The D_2h symmetrical 1,3,4,6-tetraphenylpentalenide is an excellent ligand for the stabilisation of strongly coloured bis(pentalenide) Ln^III sandwich complexes. These easily accessible compounds complement previously reported lanthanide organometallics and provide new opportunities to understand the roles of the f-orbitals in electronic structure and bonding.

C-term magnetic circular dichroism (MCD) spectroscopy is a powerful method for probing d-d and f-f transitions in paramagnetic metal complexes. However, this technique remains underdeveloped both experimentally and theoretically for studies of U(v) complexes of Oh symmetry, which have been of longstanding interest for probing electronic structure, bonding, and covalency in 5f systems. In this study, C-term NIR MCD of the Laporte forbidden f-f transitions of [UCl6]- and [UF6]- are reported, demonstrating the significant fine structure resolution possible with this technique including for the low energy Γ7 → Γ8 transitions in [UF6]-. The experimental NIR MCD studies were further extended to [U(OC6F5)6]-, [U(CH2SiMe3)6]-, and [U(NC(tBu)(Ph))6]- to evaluate the effects of ligand-type on the f-f MCD fine structure features. Theoretical calculations were conducted to determine the Laporte forbidden f-f transitions and their MCD intensity experimentally observed in the NIR spectra of the U(v) hexahalide complexes, via the inclusion of vibronic coupling, to better understand the underlying spectral fine structure features for these complexes. These spectra and simulations provide an important platform for the application of MCD spectroscopy to this widely studied class of U(v) complexes and identify areas for continued theoretical development.

A series of cerium(iv) mixed-ligand guanidinate-amide complexes, {[(Me₃Si)₂NC(N ⁱ Pr)₂] _x Ce^IV[N(SiMe₃)₂]_3-x }⁺ (x = 0-3), was prepared by chemical oxidation of the corresponding cerium(iii) complexes, where x = 1 and 2 represent novel complexes. The Ce(iv) complexes exhibited a range of intense colors, including red, black, cyan, and green. Notably, increasing the number of the guanidinate ligands from zero to three resulted in significant redshift of the absorption bands from 503 nm (2.48 eV) to 785 nm (1.58 eV) in THF. X-ray absorption near edge structure (XANES) spectra indicated increasing f occupancy (n _f) with more guanidinate ligands, and revealed the multiconfigurational ground states for all Ce(iv) complexes. Cyclic voltammetry experiments demonstrated less stabilization of the Ce(iv) oxidation state with more guanidinate ligands. Moreover, the Ce(iv) tris(guanidinate) complex exhibited temperature independent paramagnetism (TIP) arising from the small energy gap between the ground- and excited states with considerable magnetic moments. Computational analysis suggested that the origin of the low energy absorption bands was a charge transfer between guanidinate π orbitals that were close in energy to the unoccupied Ce 4f orbitals. However, the incorporation of sterically hindered guanidinate ligands inhibited optimal overlaps between Ce 5d and ligand N 2p orbitals. As a result, there was an overall decrease of ligand-to-metal donation and a less stabilized Ce(iv) oxidation state, while at the same time, more of the donated electron density ended up in the 4f shell. The results indicate that incorporating guanidinate ligands into Ce(iv) complexes gives rise to intense charge transfer bands and noteworthy electronic structures, providing insights into the stabilization of tetravalent lanthanide oxidation states.

The 4f orbitals of Ce(IV) have shown appreciably enhanced covalent mixing with ligand orbitals relative to those of Ce(III). Here, X-ray spectroscopy, magnetic susceptibility measurements, and theoretical methods are used to investigate 4f covalency in CeF62- and CeCl62-. These techniques show covalent mixing between Ce 4f and F 2p orbitals to be about 25% less than mixing between Ce 4f and Cl 3p orbitals, placing CeF62- among the most ionic Ce(IV) compounds to-date. However, ligand field analysis using the experimental data shows significantly higher 4f orbital overlap with the F 2p orbitals compared to the Cl 3p. This result is counterintuitive since the Ce-F bonds display less 4f covalency despite their higher orbital overlap, and greater overlap is traditionally associated with enhanced bond covalency. The weaker covalency is attributed to the large energy gap between Ce 4f and F 2p orbitals strongly counteracting the higher orbital overlap. These results highlight that only a concerted consideration of both atomic orbital overlap and energy matching in f-element systems leads to an accurate picture of their bonding.

5f covalency in [U(C₇H₇)₂]^- was probed with carbon K-edge X-ray absorption spectroscopy (XAS) and electronic structure theory. The results revealed U 5f orbital participation in δ-bonding in both the ground- and core-excited states; additional 5f ϕ-mixing is observed in the core-excited states. Comparisons with U(C₈H₈)₂ show greater δ-covalency for [U(C₇H₇)₂]^-.