Metallamacrocycle formation through dimerization of metal bioconjugates derived from amino acids and peptides
Celedonio M. Álvarez, Raúl García-Rodríguez and Daniel Miguel.
Dalton Trans., 2016, 45, 963-972. DOI: 10.1039/C5DT01256B


Metallamacrocycles of 12, 16, and 22 members are obtained by deprotonation of the carboxylic group of the side chain of iminopyridine complexes derived from the amino acid β-alanine, and the peptides Gly–Gly and Gly–Gly–Gly. Instead of the expected intramolecular attack to give tridentate (N,N,O) ligands, the deprotonated carboxylate attacks in an inter-molecular manner to give dimers in which the ligand acts as a bridge bonded in a κ2(N,N′) chelating fashion to one metal and as κ(O) to the other metal. The formation of the dimers is supported by NMR spectroscopy, mass spectrometry and X-ray crystallography.

Iminopyridine complexes of manganese, rhenium and molybdenum derived from amino ester methylserine, and peptides Gly-Gly, Gly-Val, and Gly-Gly-Gly Self-assembly of the peptide chain.
Celedonio M. Álvarez, Carrillo, Raúl García-Rodríguez and Daniel Miguel.
Inorg. Chem., 2012, 51, 2984-2986. DOI: 10.1021/ic2022984



Complexes containing pyridine-2-carboxaldehyde (pyca) ligand acting as κ2-(N,O) are good precursors for iminopyridine complexes derived from amino esters and peptides. In solid phase the peptide chains assemble through H-bonds adopting different patterns which depend on the geometry of the metal−ligand fragments. DOSY experiments show the H-bonding interaction between the peptide and O═PBu3.


Macrocycle Formation by Proton-Template-Induced Dimerization of Complexes with (Alkoxoimino)pyridine.
Celedonio M. Álvarez, Raúl García-Rodríguez, José M. Martín-Álvarez, Daniel Miguel and José A. Turiel
Inorg. Chem., 2012, 51, 3938-3940. DOI: 10.1021/ic300196w


proton temp ic-2012-00196w_0003


The existence of a strong hydrogen bond between two molecules of an (alkoxoimino)pyridinemanganese(I) complex induces their dimerization and the formation of a metallamacrocycle. The expected intramolecular attack of the alkoxo moiety is disfavored.


Carbonyl complexes of manganese, rhenium and molybdenum with 2-pyridylimino acid ligands.

Celedonio M. Alvarez, Raúl García-Rodríguez, Daniel Miguel
J. Organomet. Chem., 2007, 692, 5717-5726.