Rhenium(V) and Technetium(V) Oxo Complexes of an N₂N‘S Peptidic Chelator: Evidence of Interconversion between theSynandAntiConformations

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Abstract

Neutral Re(V) and Tc(V) oxo complexes of the peptide dimethylglycyl-L-seryl-L-cysteinylglycinamide (RP294) were prepared and characterized by HPLC, spectroscopic techniques, and X-ray crystallographic analysis. The peptide was prepared as a single peptide chain using solid phase methods and characterized by HPLC and various spectroscopic techniques. The water-soluble Re(V) oxo complex of dimethylglycyl-L-seryl-L-cysteinylglycinamide [ReO(RP294)] was prepared from the reaction of the peptide with either [ReO(2)(en)(2)]Cl or ReOCl(3)(PPh(3))(2) in the presence of base. The complex exists as two isomers, the serine CH(2)OH group being in the syn oranti conformation with respect to the Re-oxo bond. The ratio of the isomers at room temperature is 1:1.1. The isomers were separated by reverse-phase HPLC, but the isolation of each isomer was complicated by their rapid interconversion in aqueous solution at room temperature. The molecular structure of the syn isomer of the Re complex was determined by X-ray crystallography. Crystals of syn-[ReO(RP294)] (C(12)H(20)N(6)O(5)ReS) are orthorhombic, of space group P2(1)2(1)2(1), with a = 6.954(1) Å, b = 8.0472(1) Å, c = 32.9183(4) Å, and Z = 4. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.0327 (R(w) = 0.0838) for 10 447 reflections with I > 2sigma(I). The Re metal was coordinated in a distorted square pyramidal geometry with the oxo moiety in the apical position. The peptide coordinated to ReO(3+) via the N(amine) atom of dimethylglycine, the S(thiolate) atom of cysteine, and the two N(amide) atoms of serine and cysteine (an N(2)N'S donor atom set). The Re atom lies approximately 0.74 Å above the distorted plane formed by the N(2)N'S donor atom set. Variable-pH (1)H NMR spectral data showed the Re complex was stable from pH 5 to 8.5. The reaction of (99)TcO(4)(-) with SnCl(2), sodium gluconate, and RP294 produced the (99)Tc(V) oxo RP294 complex, [(99)TcO(RP294)]. Like the [ReO(RP294)] complex, [(99)TcO(RP294)] also exists in the syn and anti conformations in a ratio of approximately 1:1. The (99m)Tc complex of RP294 was prepared at the tracer level from the reaction of Na[(99m)TcO(4)] with excess SnCl(2), sodium gluconate, and RP294. The (99m)Tc and Re RP294 complexes behaved similarly under identical HPLC conditions.

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