0000000000243270
AUTHOR
Laura Acosta-rueda
Trapping a Highly Reactive Nonheme Iron Intermediate That Oxygenates Strong C—H Bonds with Stereoretention
An unprecedentedly reactive iron species (2) has been generated by reaction of excess peracetic acid with a mononuclear iron complex [FeII(CF3SO3)2(PyNMe3)] (1) at cryogenic temperatures, and characterized spectroscopically. Compound 2 is kinetically competent for breaking strong C-H bonds of alkanes (BDE ≈ 100 kcal·mol-1) through a hydrogen-atom transfer mechanism, and the transformations proceed with stereoretention and regioselectively, responding to bond strength, as well as to steric and polar effects. Bimolecular reaction rates are at least an order of magnitude faster than those of the most reactive synthetic high-valent nonheme oxoiron species described to date. EPR studies in tande…
Correlation between the molecular structure and the kinetics of decomposition of azamacrocyclic copper(II) complexes
The formation of copper(II) complexes with symmetrical dinucleating macrocyclic ligands containing two either monomethylated (L1) or trimethylated (L2) diethylenetriamine (Medien or Me3dien) subunits linked by pyridine spacers has been studied by potentiometry. Potentiometric studies show that L1 has larger basicity than L2 as well as higher stability of its mono- and binuclear complexes. The crystal structures of L1·6HCl (1), [Cu2(L1)Cl2](CF3SO3)2 (2), [Cu2(L1)(OH)](ClO4)3·3H2O (3) and [Cu(L1)](ClO4)2 (4) show that L1 adopts different coordination modes when bound to copper(II). Whereas in 2, each copper(II) is bound to one Medien subunit and to one pyridine group, in 3 each metal center i…
Iron(II) Complexes with Scorpiand-Like Macrocyclic Polyamines: Kinetico-Mechanistic Aspects of Complex Formation and Oxidative Dehydrogenation of Coordinated Amines.
The Fe(II) coordination chemistry of a pyridinophane tren-derived scorpiand type ligand containing a pyridine ring in the pendant arm is explored by potentiometry, X-ray, NMR, and kinetics methods. Equilibrium studies in water show the formation of a stable [FeL]2+ complex that converts to monoprotonated and monohydroxylated species when the pH is changed. A [Fe(H–2L)]2+ complex containing an hexacoordinated dehydrogenated ligand has been isolated, and its crystal structure shows the formation of an imine bond involving the aliphatic nitrogen of the pendant arm. This complex is low spin Fe(II) both in the solid state and in solution, as revealed by the Fe–N bond lengths and by the NMR spect…
Equilibrium, Kinetic, and Computational Studies on the Formation of Cu2+ and Zn2+ Complexes with an Indazole-Containing Azamacrocyclic Scorpiand: Evidence for Metal-Induced Tautomerism
Cu(2+) and Zn(2+) coordination chemistry of a new member of the family of scorpiand-like macrocyclic ligands derived from tris(2-aminoethyl)amine (tren) is reported. The new ligand (L1) contains in its pendant arm not only the amine group derived from tren but also a 6-indazole ring. Potentiometric studies allow the determination of four protonation constants. UV-vis and fluorescence data support that the last protonation step occurs on the indazole group. Equilibrium measurements in the presence of Cu(2+) and Zn(2+) reveal the formation of stable [ML1](2+), [MHL1](3+), and [ML1(OH)](+) complexes. Kinetic studies on the acid-promoted decomposition of the metal complexes were carried out usi…
CCDC 1009322: Experimental Crystal Structure Determination
Related Article: Laura Acosta-Rueda, Estefanía Delgado-Pinar, Javier Pitarch-Jarque, Alexis Rodríguez, Salvador Blasco, Jorge González, Manuel G. Basallote, Enrique García-España|2015|Dalton Trans.|44|8255|doi:10.1039/C5DT00408J
CCDC 1521794: Experimental Crystal Structure Determination
Related Article: M. Paz Clares, Laura Acosta-Rueda, Carmen E. Castillo, Salvador Blasco, Hermas R. Jiménez, Enrique García-España, and Manuel G. Basallote|2017|Inorg.Chem.|56|4400|doi:10.1021/acs.inorgchem.6b03070
CCDC 1009323: Experimental Crystal Structure Determination
Related Article: Laura Acosta-Rueda, Estefanía Delgado-Pinar, Javier Pitarch-Jarque, Alexis Rodríguez, Salvador Blasco, Jorge González, Manuel G. Basallote, Enrique García-España|2015|Dalton Trans.|44|8255|doi:10.1039/C5DT00408J
CCDC 1009325: Experimental Crystal Structure Determination
Related Article: Laura Acosta-Rueda, Estefanía Delgado-Pinar, Javier Pitarch-Jarque, Alexis Rodríguez, Salvador Blasco, Jorge González, Manuel G. Basallote, Enrique García-España|2015|Dalton Trans.|44|8255|doi:10.1039/C5DT00408J
CCDC 1036385: Experimental Crystal Structure Determination
Related Article: Joan Serrano-Plana, Williamson N. Oloo, Laura Acosta-Rueda, Katlyn K. Meier, Begoña Verdejo, Enrique García-España, Manuel G. Basallote, Eckard Münck, Lawrence Que Junior, Anna Company, and Miquel Costas|2015|J.Am.Chem.Soc.|137|15833|doi:10.1021/jacs.5b09904
CCDC 1446018: Experimental Crystal Structure Determination
Related Article: Joan Serrano-Plana, Williamson N. Oloo, Laura Acosta-Rueda, Katlyn K. Meier, Begoña Verdejo, Enrique García-España, Manuel G. Basallote, Eckard Münck, Lawrence Que Junior, Anna Company, and Miquel Costas|2015|J.Am.Chem.Soc.|137|15833|doi:10.1021/jacs.5b09904
CCDC 1009324: Experimental Crystal Structure Determination
Related Article: Laura Acosta-Rueda, Estefanía Delgado-Pinar, Javier Pitarch-Jarque, Alexis Rodríguez, Salvador Blasco, Jorge González, Manuel G. Basallote, Enrique García-España|2015|Dalton Trans.|44|8255|doi:10.1039/C5DT00408J