Beryllium (II) complexes of the klaui tripodal ligand cyclopentadienyltris (diethylphosphito-P) cobaltate(-)

The interactions of the beryllium(II) ion with the cyclopentadienyltris(diethylphosphito-P)cobaltate monoanion, L^-, have been investigated, in aqueous solution, by synthetic methods, potentiometry, ESMS, and ¹H, ³¹P, and ⁹Be NMR spectroscopy. L^- has been found able to displace either two or three water molecules in the beryllium(II) coordination sphere, to form mononuclear, dinuclear, and trinuclear derivatives, in which the metal ion is pseudotetrahedrally coordinated. The species [BeL(H₂O)]⁺ and [Be₂L₂(μ-OH)]⁺ have been identified in solution while complexes of formula BeL₂ and [Be₃L₄](ClO₄)₂ have been isolated as solid materials. The species [BeL(OPPh₂)]⁺, closely related to [BeL(H₂O)]⁺, has been characterized in acetone solution and isolated as tetraphenylborate salt. The structure of the unusual trimeric complex [Be₃L₄]²⁺ has been elucidated by an unprecedented 2D ⁹Be-³¹P NMR correlation spectrum showing the presence of a single central beryllium nucleus and two equivalent terminal beryllium nuclei. The three beryllium centers are held together by four cobaltate ligands, which display two different bonding modes: two ligands are terminally linked with all the three oxygen donors to one terminal beryllium, and the other two bridge two metal centers, sharing the oxygen donors between central and terminal beryllium atoms.

Applications of scanning electrochemical microscopy (SECM) for local characterization of AZ31 surface during corrosion in a buffered media

Different modes of scanning electrochemical mapping (SECM) such as surface generation/tip collection (SG/TC), amperometry, AC-SECM and potentiometry were employed to characterize the active/passive domains, hydrogen gas (H2) evolution and local pH on a corroding surface of AZ31 in simulated biological fluid (SBF). It was found that the main domains of H2 evolution are associated with lower insulating properties of the surface as well as higher local pH. The near surface pH was found to be highly alkaline indicating that, even in a buffered solution such as SBF, the local pH on a corroding AZ31 surface can be significantly different to the bulk pH. © 2014 Elsevier Ltd.