TY - JOUR
T1 - Understand, elucidate and rationalize the coordination mode of pyrimidylmethylamines
T2 - An intertwined study combining NMR and DFT methods
AU - Herbert Pucheta, J. E.
AU - Candy, M.
AU - Colin, O.
AU - Requet, A.
AU - Bourdreux, F.
AU - Galmiche-Loire, E.
AU - Gaucher, A.
AU - Thomassigny, C.
AU - Prim, D.
AU - Mahfoudh, M.
AU - Leclerc, E.
AU - Campagne, J. M.
AU - Farjon, J.
N1 - Publisher Copyright:
© 2015 the Owner Societies.
PY - 2015/4/14
Y1 - 2015/4/14
N2 - Conception of new pyrimidylmethylamine (pyrma) ligands and their corresponding Pd(ii) complexes has been described. Both symmetrical and non-symmetrical ligands were prepared and subjected to complexation. Two different coordination modes, Pd(N,N)- or Pd(C,N,N)-pyrma, have been evidenced depending on the substitution of the pyrimidine ring and the nature or the shape of the additional pendant arm. In a non-symmetrical pyrimidine series, the substituent-induced discrimination of each heterocyclic nitrogen atom provoked regio-controlled coordination to the metal center. The molecular structure of pyrma-Pd(ii) complexes in the solution state has been elucidated thanks to combined NMR experiments and DFT calculations. This study highlights the potency of 15N and 13C NMR spectroscopy for the elucidation of the regio-selective coordination to the Pd(ii) in the pyrma-based complex series. DFT calculations were highly relevant to the identification of crucial factors that govern the regio-selectivity and the complexation modes. Close predicted and experimental chemical shift values put into relief the reliability of coordination modes for the most stable complexes in solution, depicted by DFT approaches.
AB - Conception of new pyrimidylmethylamine (pyrma) ligands and their corresponding Pd(ii) complexes has been described. Both symmetrical and non-symmetrical ligands were prepared and subjected to complexation. Two different coordination modes, Pd(N,N)- or Pd(C,N,N)-pyrma, have been evidenced depending on the substitution of the pyrimidine ring and the nature or the shape of the additional pendant arm. In a non-symmetrical pyrimidine series, the substituent-induced discrimination of each heterocyclic nitrogen atom provoked regio-controlled coordination to the metal center. The molecular structure of pyrma-Pd(ii) complexes in the solution state has been elucidated thanks to combined NMR experiments and DFT calculations. This study highlights the potency of 15N and 13C NMR spectroscopy for the elucidation of the regio-selective coordination to the Pd(ii) in the pyrma-based complex series. DFT calculations were highly relevant to the identification of crucial factors that govern the regio-selectivity and the complexation modes. Close predicted and experimental chemical shift values put into relief the reliability of coordination modes for the most stable complexes in solution, depicted by DFT approaches.
UR - http://www.scopus.com/inward/record.url?scp=84961312211&partnerID=8YFLogxK
U2 - 10.1039/c5cp00241a
DO - 10.1039/c5cp00241a
M3 - Artículo
AN - SCOPUS:84961312211
SN - 1463-9076
VL - 17
SP - 8740
EP - 8749
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 14
ER -