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Spectroscopic evidence of forming a fused boron heterocyclic radical through photoinduced boron atom insertion has been presented. Atom colors: B = pink; C = gray; H = white.

Strategies of matrix-isolation and finding cases with stronger-coupling were adopted to demonstrate the splitting theory.

Boron heterocyclic radicals: spectroscopic evidence of forming a six-membered ring 3,4,5-trihydroborinine radical and a five-membered ring 1-methyl-2-dihydro-1H-borole radical in solid neon has been presented. Atom colors: B = pink; C = gray; and H = white.

Spectroscopic evidence of forming a silole derivative directly through the reaction of atomic silicon with benzene presented for the first time.

The anions pertechnetate, TcO4-, and perrhenate, ReO4-, exhibit very similar chemical and physical properties. Revealing and understanding disparities between them enhances fundamental understanding of both. Electrospray ionization generated the gas-phase proton bound dimer (TcO4-)(H+)(ReO4-). Collision induced dissociation of the dimer yielded predominantly HTcO4 and ReO4-, which according to Cooks' kinetic method indicates that the proton affinity (PA) of TcO4- is greater than that of ReO4-. Density functional theory computations agree with the experimental observation, providing PA[TcO4-] = 300.1 kcal mol-1 and PA[ReO4-] = 297.2 kcal mol-1. Attempts to rationalize these relative PAs based on elementary molecular parameters such as atomic charges indicate that the entirety of bond formation and concomitant bond disruption needs to be considered to understand the energies associated with such protonation processes. Although in both the gas and solution phases, TcO4- is a stronger base than ReO4-, it is noted that the significance of even such qualitative accordance is tempered by the very different natures of the underlying phenomena.

Electrospray ionization of solutions containing a tripodal hydroxylamine ligand, H3TriNOx ([((2-tBuNOH)C6H4CH2)3N]) denoted as L, and a hydrogen halide HX: HCl, HBr and/or HI, yielded gas-phase anion complexes [L(X)]- and [L(HX2)]-. Collision induced dissociation (CID) of mixed-halide complexes, [L(HXaXb)]-, indicated highest affinity for I- and lowest for Cl-. Structures and energetics computed by density functional theory are in accord with the CID results, and indicate that the gas-phase binding preference is a manifestation of differing stabilities of the HX molecules. A high halide affinity of [L(H)]+ in solution was also demonstrated, though with a highest preference for Cl- and lowest for I-, the opposite observation of, but not in conflict with, what is observed in gas phase. The results suggest a connection between gas- and condensed-phase chemistry and computational approaches, and shed light on the aggregation and anion recognition properties of hydroxylamine receptors.

Selectivity for An(iii) vs. Ln(iii) binding and extraction using dipicolinamide analogs containing the C[double bond, length as m-dash]O vs. C[double bond, length as m-dash]S groups was investigated in solution and the gas-phase, and by DFT calculations. The results show higher selectivity for complex formation and extraction for Am(iii) vs. Eu(iii) for the softer dithioamide vs. the diamide ligand, while in CH3CN the diamide binds more strongly than the thioamide to several Ln(iii), forming 1 : 1 complexes.

The experimentally known highest oxidation state of iron has been determined to be Fe(VI) so far. Here we report a combined matrix-isolation infrared spectroscopic and theoretical study of two interconvertible iron oxide anions: a dioxoiron peroxide complex [(η2-O2)FeO2]− with a C2v-structure and a tetroxide FeO4− with a D2d tetrahedral structure, which are formed by co-condensation of laser-ablated iron atoms and electrons with O2/Ar mixtures at 4 K. Quantum chemistry theoretical studies indicate that the Jahn–Teller distorted tetroxide FeO4− anion is a d1 species with hereto the highest iron formal oxidation state Fe(VII).