A New Donor Atom System [(SNN)(S)] for the Synthesis of Neutral Oxotechnetium(V) Mixed-Ligand Complexes |
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Authors: | Papadopoulos M S Pelecanou M Pirmettis I C Spyriounis D M Raptopoulou C P Terzis A Stassinopoulou C I Chiotellis E |
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Institution: | Institutes of Radioisotopes-Radiodiagnostic Products, Biology, and Materials Science, NCSR "Demokritos", P.O. Box 60228, 15310 Aghia Paraskevi, Athens, Greece. |
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Abstract: | A new approach to the "3 + 1" mixed ligand oxotechnetium complexes of the general formula TcOL1L2, with ligands (L1H(2)) containing the SNN donor set and various monodentate thiols as coligands (L2H) is reported. The ligands L1H(2) (1-3, general formula R(1)CH(2)CH(2)NHCH(2)C(R(2))(2)SH where R(1) = N(CH(3))(2) and R(2) = H in 1, R(1) = pyrrolidin-1-yl and R(2) = H in 2, and R(1) = piperidin-1-yl and R(2) = CH(3) in 3) act as tridentate SNN chelates to the TcO(3+) core, leaving open one coordination site cis to the oxo group. In the presence of a monodentate thiol (L2H) and using (99)Tc(V)-gluconate as precursor, the vacancy is filled by the thiol which acts as the coligand. With this approach four neutral oxotechnetium complexes (4-7, general formula TcOR(1)CH(2)CH(2)NCH(2)C(R(2))(2)S]SR] where RSH = p-methoxybenzenethiol, or p-methylbenzenethiol or benzyl mercaptan) were prepared in high yield by reacting L1H(2) and L2H with Tc(V)-gluconate in a ratio 1:1:1. The complexes were characterized by elemental analysis and spectroscopic methods. Complete assignments of (1)H and (13)C NMR resonances were made for all complexes. X-ray crystallographic studies of 5 (R(1) = pyrrolidin-1-yl, R(2) = H, RSH = p-methylbenzenethiol) and 7 (R(1) = piperidin-1-yl, R(2) = CH(3), RSH = benzyl mercaptan) showed that the complexes crystallize in the monoclinic space group P2(1)/n (a = 10.223(1) ?, b = 9.283(1) ?, c = 18.337(2) ?, beta = 97.262(2) degrees, V = 1726.3(4) ?(3), Z = 4; a = 11.876(2) ?, b = 10.470(2) ?, c = 17.098(3) ?, beta = 105.990(4) degrees, V = 2043.8(6) ?(3), Z = 4, for 5 and 7, respectively). Complexes5 and 7 have distorted square pyramidal coordination geometry with the oxo ligand in the axial position. The steric requirements of the oxo group cause the Tc atom to be displaced 0.68 ? out of the mean equatorial plane of the NNSS donor atoms in both complexes. |
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