Three new mononuclear oxovanadium(IV) complexes [VO(acac)(R-BIAN)]Cl (BIAN = 1,2-bis{(R-phenyl)imino}acenaphthene, R = H, 1; CH₃, 2; Cl, 3) were prepared and characterized. They promoted the catalytic oxidation of olefins such as cyclohexene, cis-cyclooctene, and styrene with both tbhp (tert-butylhydroperoxide) and H₂O₂, and of enantiopure olefins (S(−)- and R(+)-pinene, and S(−)- and R(+)-limonene) selectively to their epoxides, with tbhp as the oxidant. The TOFs for styrene epoxidation promoted by complex 3 with H₂O₂ (290 mol mol⁻¹ _V h⁻¹) and for cis-cyclooctene epoxidation by 2 with tbhp (248 mol mol⁻¹ _V h⁻¹) are particularly good. Conversions reached 90% for several systems with tbhp, and were lower with H₂O₂. A preference for the internal CC bond, rather than the terminal one, was found for limonene. Kinetic data indicate an associative process as the first step of the reaction and complex [VO(acac)(H-BIAN)]⁺ (1⁺) was isolated in an FTICR cell after adding tbhp to 1. EPR studies provide evidence for the presence of a V(IV) species in solution, until at least 48 hours after the addition of tbhp and cis-cyclooctene, and cyclic voltammetry studies revealed an oxidation potential above 1 V for complex 1. DFT calculations suggest that a [VO(H-BIAN)(MeOO)]⁺ complex is the likely active V(IV) species in the catalytic cycle from which two competitive mechanisms for the reaction proceed, an outer sphere path with an external attack of the olefin at the coordinated peroxide, and an inner sphere mechanism starting with a complex with the olefin coordinated to vanadium.

Several ferrocene derivatives (five mononuclear and two binuclear), including the new N-(p-chlorophenyl)-carboxamidoferrocene (1), were synthesized and their anticancer activity investigated. Two of them, 3 and 7, bearing a benzimidazole backbone were the most active against HeLa cells achieving IC₅₀ values of ~5 μM along with 4 with a dipyridylamine ligand (~6 μM). Complex 6, also with a benzimidazole backbone, displayed slightly higher values (~11 μM). Cyclic voltammetry studies show that while the non-cytotoxic ferrocene derivatives 1, 2, and 5 follow a ferrocene-based redox behavior, derivatives 3, 4, 6, and 7 exhibit a more complex mechanism. These complex mechanisms are consistent with a more effective cytotoxic activity. Mössbauer spectroscopy parameters reflect a very small influence of the substituents.

Single ion magnet behaviour is reported for a mononuclear Mn(III) ion with tridentate Schiff-base ligands which exhibits a tetragonal Jahn–Teller elongation along the N_amine–Mn–N_amine axis and crystallises with two crystallographically distinct Mn(III) cations (unit A and unit B). While magnetic measurements show a large and negative axial zero-field splitting (D = −4.73 cm⁻¹), HF-EPR reveal two distinct large axial Ds (D = −4.60 cm⁻¹ for unit A and D = −4.18 cm⁻¹ for unit B), thus resulting in the largest D known to date for a Mn(III) single ion magnet. AC magnetic measurements at 2000 Oe allowed determination of the energy barrier for spin reversal (10.19 K) and spin reversal relaxation time (1.476 × 10⁻⁶ s) for the Mn(III) ion. Computational studies were used to characterise the electronic structure and substantiate the zero field splitting in the Mn(III) complex.

The reaction of coordinatively unsaturated Co(II) PCP pincer complexes with nitric oxide leads to the formation of new, air-stable, diamagnetic mono nitrosyl compounds. The synthesis and characterization of five- and four-coordinate Co(III) and Co(I) nitrosyl pincer complexes based on three different ligand scaffolds is described. Passing NO through a solution of [Co(PCP^NMe-iPr)Cl], [Co(PCP^O-iPr)Cl] or [Co(PCP^CH2-iPr)Br] led to the formation of the low-spin complex [Co(PCP-iPr)(NO)X] with a strongly bent NO ligand. Treatment of the latter species with (X = Cl, Br) AgBF₄ led to chloride abstraction and formation of cationic square-planar Co(I) complexes of the type [Co(PCP-iPr)(NO)]⁺ featuring a linear NO group. This reaction could be viewed as a formal two electron reduction of the metal center by the NO radical from Co(III) to Co(I), if NO is counted as NO⁺. Hence, these systems can be described as {CoNO}⁸ according to the Enemark–Feltham convention. X-ray structures, spectroscopic and electrochemical data of all nitrosyl complexes are presented. Preliminary studies show that [Co(PCP^NMe-iPr)(NO)]⁺ catalyzes efficiently the reductive hydroboration of nitriles with pinacolborane (HBpin) forming an intermediate {CoNO}⁸ hydride species.