The PN2S chelate N-[N-(3-diphenylphosphinopropionyl)glycyl]-S-tritylcysteine methyl ester [PN2S(Trt)-OMe] was synthesized and reacted with ReOCl3(PPh3)(2) and Ph4P[ReOCl4]. The reactions of both tritylated and detritylated ligands with (ReO)-O-V precursors gave two diastereomers, 9a and 9b, of the ReO(PN2S-OMe) complex. The two isomers, produced in a 1:1 molar ratio, are stable and do not interconvert. They were separated by reverse-phase HPLC and characterized by NMR, FT-IR, and UV-visible spectroscopy and electrospray mass spectrometry. X-ray analysis established for 9a the presence in the solid of the syn isomer. Compound 9a, C21H23N2O5PSRe, crystallized from warm acetonitrile in the triclinic space group P (1) over bar, a = 9.828(2) Angstrom, b = 11.163(2) Angstrom, c = 11.641(2) Angstrom, alpha = 106.48(3)degrees, beta = 109.06(3)degrees, gamma = 102.81(3)degrees, V = 1085.7(4) Angstrom(3), Z = 2. The PN2S coordination set is in the equatorial plane, and the complex shows a distorted square pyramidal coordination. The anti configuration assigned to 9b is consistent with all the available physicochemical data. Follow-up of the reaction of the detritylated ligand with Ph4P[ReOCl4] in ethanol or acetonitrile indicated that the phosphorus atom of the chelate binds first to the metal and that this bond acts as the driving force for coordination.
Synthesis and characterization of rhenium(V) oxo complexes with N-[N-(3-diphenylphosphinopropionyl)glycyl]cysteine methyl ester. X-ray crystal structure of {ReO[Ph2P(CH2)(2)C(O)-Gly-Cys-OMe(P,N,N,S)]}
VISENTIN, ROBERTA;ROSSIN, RAFFAELLA;GIRON, MARIA CECILIA;DOLMELLA, ALESSANDRO;BANDOLI, GIULIANO;MAZZI, ULDERICO
2003
Abstract
The PN2S chelate N-[N-(3-diphenylphosphinopropionyl)glycyl]-S-tritylcysteine methyl ester [PN2S(Trt)-OMe] was synthesized and reacted with ReOCl3(PPh3)(2) and Ph4P[ReOCl4]. The reactions of both tritylated and detritylated ligands with (ReO)-O-V precursors gave two diastereomers, 9a and 9b, of the ReO(PN2S-OMe) complex. The two isomers, produced in a 1:1 molar ratio, are stable and do not interconvert. They were separated by reverse-phase HPLC and characterized by NMR, FT-IR, and UV-visible spectroscopy and electrospray mass spectrometry. X-ray analysis established for 9a the presence in the solid of the syn isomer. Compound 9a, C21H23N2O5PSRe, crystallized from warm acetonitrile in the triclinic space group P (1) over bar, a = 9.828(2) Angstrom, b = 11.163(2) Angstrom, c = 11.641(2) Angstrom, alpha = 106.48(3)degrees, beta = 109.06(3)degrees, gamma = 102.81(3)degrees, V = 1085.7(4) Angstrom(3), Z = 2. The PN2S coordination set is in the equatorial plane, and the complex shows a distorted square pyramidal coordination. The anti configuration assigned to 9b is consistent with all the available physicochemical data. Follow-up of the reaction of the detritylated ligand with Ph4P[ReOCl4] in ethanol or acetonitrile indicated that the phosphorus atom of the chelate binds first to the metal and that this bond acts as the driving force for coordination.Pubblicazioni consigliate
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