Ismael Nieto

Thermodynamics of hydrogen atom transfer to a high-valent iron imido complex.

Thermodynamic investigations relevant to hydrogen atom transfer by the high-valent iron imido complex [LMesFe[triple bond]NAd]OTf have been undertaken. The complex is found to be weakly oxidizing by cyclic voltammetry (E1/2 = -0.98 V vs Cp2Fe+/Cp2Fe in MeCN). A combination of experimental and computational studies has been used to determine the acidity of LMesFe-N(H)Ad+ (pKa = 37 in MeCN), allowing the N-H BDFE (88(5) kcal/mol) to be calculated from a thermodynamic cycle. Consistent with this value, [LMesFe[triple bond]NAd]OTf reacts with 9,10-dihydroanthracene (C-H BDE = 78(1) kcal/mol) to form anthracene.

Crystal structures of bis- and hexakis[(6,6'-di-hydroxy-bipyridine)copper(II)] nitrate coordination complexes.

Two copper(II) complexes, a dinuclear and a hexanuclear complex with bridging hydroxyl and nitrate ligands, were obtained from reaction of copper nitrate with dihydroxybipyridine at neutral and slightly acidic pH. Formation of multi-nuclear complexes contrasts with the equivalent sulfate compounds which formed discrete mononuclear complexes. The complexes feature intramolecular and intermolecular hydrogen bonding.

A new synthetic route to bulky “second generation” tris(imidazol-2-ylidene)borate ligands: synthesis of a four coordinate iron(II) complex

A bulky tripodal tris(carbene)borate ligand, prepared from 1-tert-butylimidazole, is cleanly transferred to iron(II) by a magnesium reagent.