Hydrogen and copper ion induced molecular reorganizations in two new scorpiand-like ligands appended with pyridine rings.
The synthesis of two new ligands constituted of a tris(2-aminoethyl)amine moiety linked to the 2,6 positions of a pyridine spacer through methylene groups in which the hanging arm is further functionalized with a 2-pycolyl (L1) or 3-pycolyl (L2) group is presented. The protonation of L1 and L2 and formation of Cu(2+) complexes have been studied using potentiometric, NMR, X-ray, and kinetic experiments. The results provide new information about the relevance of molecular movements in the chemistry of this kind of so-called scorpiand ligand. The comparison between these two ligands that only differ in the position of the substituent at the arm reveals important differences in both thermodynamic and kinetic properties. The Cu(2+) complex with L1 is several orders of magnitude more stable than that with L2, surely because in the latter case the pyridine nitrogen at the pendant arm is unable to coordinate to the metal ion with the ligand acting as hexadentate, a possibility that occurs in the case of [CuL1](2+), as demonstrated by its crystal structure. Significant differences are also found between both ligands in the kinetic studies of complex formation and decomposition. For L1, those processes occur in a single kinetic step, whereas for L2 they occur with the formation of a detectable reaction intermediate whose structure corresponds to that resulting from the movement typical of scorpiands. Another interesting conclusion derived from kinetic studies on complex formation is that the reactive form of the ligand is H(3)L(3+) for L1 and H(2)L(2+) for L2. DFT calculations are also reported, and they allow a rationalization of the kinetic results relative to the reactive forms of the ligands in the process of complex formation. In addition, they provide a full picture of the mechanistic pathway leading to the formation of the first Cu-N bond, including outer-sphere complexation, water dissociation, and reorganization of the outer-sphere complex.
Blasco
Salvador
S
Departamento de Química, Inorgánica, Universidad de Valencia, Instituto de Ciencia Molecular, Edificio de Institutos de Paterna Apdo 22085, 46071, Valencia, Spain.
Verdejo
Begoña
B
Clares
M Paz
MP
Castillo
Carmen E
CE
Algarra
Andrés G
AG
Latorre
Julio
J
Máñez
M Angeles
MA
Basallote
Manuel G
MG
Soriano
Conxa
C
García-España
Enrique
E
D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006859:Hydrogen / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*
D008024:Ligands; D009942:Organometallic Compounds; D011725:Pyridines; D003300:Copper; D006859:Hydrogen; C023666:pyridine