The use of a sterically hindered diamine ligand (Me4DACH) has allowed for the first time, the isolation and characterization, both in the solid state (X-ray crystallography) and in solution (circular dichroism), of pure ΔHT rotamers of [Pt(Me4dach)(5′-GMP)2] (compounds 1 and 2 for R,R and S,S configurations of the Me4DACH ligand, respectively). Comparison of the CD spectra obtained for each rotamer, which differ only in the chirality of the Me4DACH ligand (R,R or S,S) or in the chirality of the HT conformation (Δ or Λ), allowed us to conclude that, in the 200-350 nm range, the contributions to the overall CD spectrum that stem from diamine chirality and diamine-induced chirality of platinum dd transitions or from sugar chirality are negligible relative to the exciton chiral coupling that occurs for π-π* transitions of the cis guanines. Accurate molecular structures of 1•10D2O and 2•14D2O (conventional crystallographic agreement indexes R1 convergent to 2.07% and 2.18%, respectively) revealed that the crystallized rotamers have a ΔHT conformation that is in agreement with all previously reported X-ray structures of [Pt(diamine)(nucleos(t)ide) 2] complexes. This conformation allows the 5′-phosphate to be located in proximity to the Me4DACH ligand so that (P)O⋯HC(N) hydrogen-bond interactions exists in both complexes. For both structures, the canting of the guanine planes on the coordination plane is right-handed (R; canting angle (φ) of 80.9° and 73.2°, respectively); this indicates that the canting direction is driven by the HT conformation chirality (Δ for both compounds) and not by the chirality of the carrier ligand (different for the two compounds). Density functional theory analysis of the conformational space as a function of φ indicated a good agreement between the computed and experimental structures. The increase in energy for φ values below 65° and 55° (for 1 and 2, respectively) is mainly due to the short intramolecular contacts between C(8)H and the cis N-Me groups on the same side of the platinum coordination plane.

X-ray Structure and Circular Dichroism of Pure Rotamers of Bis[guanosine-5′-monophosphate(-1)](N,N,N′,N,′-tetramethylcyclohexyl-1,2-diamine)platinum(II) Complexes That Have R,R and S,S Configurations at the Asymmetric Diamine

BENEDETTI, MICHELE;
2003

Abstract

The use of a sterically hindered diamine ligand (Me4DACH) has allowed for the first time, the isolation and characterization, both in the solid state (X-ray crystallography) and in solution (circular dichroism), of pure ΔHT rotamers of [Pt(Me4dach)(5′-GMP)2] (compounds 1 and 2 for R,R and S,S configurations of the Me4DACH ligand, respectively). Comparison of the CD spectra obtained for each rotamer, which differ only in the chirality of the Me4DACH ligand (R,R or S,S) or in the chirality of the HT conformation (Δ or Λ), allowed us to conclude that, in the 200-350 nm range, the contributions to the overall CD spectrum that stem from diamine chirality and diamine-induced chirality of platinum dd transitions or from sugar chirality are negligible relative to the exciton chiral coupling that occurs for π-π* transitions of the cis guanines. Accurate molecular structures of 1•10D2O and 2•14D2O (conventional crystallographic agreement indexes R1 convergent to 2.07% and 2.18%, respectively) revealed that the crystallized rotamers have a ΔHT conformation that is in agreement with all previously reported X-ray structures of [Pt(diamine)(nucleos(t)ide) 2] complexes. This conformation allows the 5′-phosphate to be located in proximity to the Me4DACH ligand so that (P)O⋯HC(N) hydrogen-bond interactions exists in both complexes. For both structures, the canting of the guanine planes on the coordination plane is right-handed (R; canting angle (φ) of 80.9° and 73.2°, respectively); this indicates that the canting direction is driven by the HT conformation chirality (Δ for both compounds) and not by the chirality of the carrier ligand (different for the two compounds). Density functional theory analysis of the conformational space as a function of φ indicated a good agreement between the computed and experimental structures. The increase in energy for φ values below 65° and 55° (for 1 and 2, respectively) is mainly due to the short intramolecular contacts between C(8)H and the cis N-Me groups on the same side of the platinum coordination plane.
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11587/105935
 Attenzione

Attenzione! I dati visualizzati non sono stati sottoposti a validazione da parte dell'ateneo

Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 27
  • ???jsp.display-item.citation.isi??? 27
social impact