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Multinuclear 1D and 2D NMR Investigations on the Interaction between the Pyrimidic Nucleotides 5′‐CMP, 5′‐dCMP, and 5′‐UMP and Diethyltin Dichloride in Aqueous Medium
Author(s) -
Ghys Laurent,
Biesemans Monique,
Gielen Marcel,
Garoufis Achilleas,
Hadjiliadis Nick,
Willem Rudolph,
Martins José C.
Publication year - 2000
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(200003)2000:3<513::aid-ejic513>3.0.co;2-m
Subject(s) - chemistry , moiety , aqueous solution , nuclear magnetic resonance spectroscopy , nucleotide , tin , crystallography , molecule , phosphate , electrospray ionization , stereochemistry , inorganic chemistry , mass spectrometry , medicinal chemistry , organic chemistry , biochemistry , gene , chromatography
The interactions between diethyltin dichloride and 5′‐CMP, 5′‐dCMP, and 5′‐UMP in aqueous solution were investigated by multinuclear 1D and 2D NMR techniques including 119 Sn, 15 N and 31 P nuclei. These studies were combined with electrospray mass spectrometry, infrared spectroscopy, solid state 13 C, 31 P and 117 Sn CP‐MAS NMR, and elemental analysis. As demonstrated by 31 P‐ 1 H HOESY spectroscopy, the diethyltin moiety interacts with the phosphate group of the pyrimidic mononucleotides in the pH range 0.5–3.5. Compound 8 (X = Cl), the solid isolated in this pH range from 5′‐CMP, contains two tin atoms bridged by one oxygen and one chlorine atom, each tin atom being linked to the phosphate group of a nucleotide moiety. For 5′‐UMP the solid isolated ( 12 ) has a dimeric structure with two different tin atoms; it can be formed by dimerization of compound 11 with the elimination of two water molecules. As demonstrated by 1 H‐ 119 Sn HMQC correlation NMR data and the 2 J ( 119 Sn–O– 117 Sn) coupling constant of 156 Hz, the diethyltin moiety reacts with the O(2′) and O(3′) oxygen atoms of the nucleotides to form a dimeric diethyldioxastannolane at pH > 9.0. Between pH 5.0 and 9.0, no evidence for any interaction between the diethyltin moiety and the nucleotides was found.