title: Complexes of Zn(2+), Cd(2+), and Hg(2+) with 2-(alpha-Hydroxybenzyl)thiamine Monophosphate Chloride.
abstract: The binding sites of Zn(2+), Cd(2+), and Hg(2+) in complexes with 2-(alpha-hydroxybenzyl)thiamine monophosphate chloride, (LH)(+)Cl(-), have been investigated in the solid state [2-(alpha-hydroxybenzyl)thiamin monophosphate chloride monoprotonated at the phosphate group and protonated at N(1)' is denoted as (LH)(+)Cl(-); therefore, the ligand monoprotonated at the phosphate group and deprotonated at N(1)' is L]. Complexes of formulae MLCl(2), M(LH)Cl(3), and (MCl(4))(2)(-)(LH)(2)(+) (M = Zn(2+), Cd(2+), and Hg(2+)) were isolated in aqueous and methanolic solutions, depending on pH. The crystal structure of the complex of formula HgL(2)Cl(2) was solved, together with that of the free ligand (LH)(+)Cl(-), by X-ray crystallography. HgL(2)Cl(2) crystallizes in C2/c, with a = 32.968(6) Å, b = 7.477(2) Å, c = 21.471(4) Å, beta = 118.19(1) degrees, V = 4665(2) Å(3), and Z = 4. (LH)(+)Cl(-) crystallizes in Cc, with a = 10.951(3) Å, b = 17.579(4) Å, c = 13.373(3) Å, beta = 105.36(2) degrees, V = 2482.4(10) Å(3), and Z = 4. Mercury(II) binds to the N(1') of the pyrimidine ring. Both ligands are in the S conformation [Phi(T) = -98.1(9) degrees and Phi(P) = 176.1(10) degrees for HgL(2)Cl(2) and Phi(T) = 104.1(5) degrees and Phi(P) = 171.9(6) degrees for (LH)(+)Cl(-)]. (31)P and (13)C NMR spectra, together with vibrational spectra (IR/Raman), are used to deduce the binding sites of the metal and the protonation states of the ligand at various pH values. It is found that solid-state (31)P NMR spectroscopy is particularly useful in characterizing these complexes as the (31)P shielding tensors are sensitive to the state of the phosphate group. On the other hand, the (31)P NMR spectra indicate that direct bonding between Zn(2+) and Cd(2+) to the phosphate can occur under certain preparation conditions. Solid-state (13)C NMR and vibrational (IR/Raman) spectroscopic results are also in agreement with the other techniques.
authors.affiliation: Department of Chemistry, University of Ioannina, Ioannina 45-110, Greece, Department of Chemistry, University of Southern California, Los Angeles, California 90089-1062, Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, PQ, H3A 2K6 Canada, and Department of Chemistry, University College London, 20 Gordon Street, London WC1H OAJ, U.K.
authors.forename: Katerina
authors.initials: K
authors.lastname: Dodi
authors.forename: Ioannis P.
authors.initials: IP
authors.lastname: Gerothanassis
authors.forename: Nick
authors.initials: N
authors.lastname: Hadjiliadis
authors.forename: Andre
authors.initials: A
authors.lastname: Schreiber
authors.forename: Robert
authors.initials: R
authors.lastname: Bau
authors.forename: Ian S.
authors.initials: IS
authors.lastname: Butler
authors.forename: Patrick J.
authors.initials: PJ
authors.lastname: Barrie