Preparation and structural studies of neutral oxorhenium(V) complexes with D-penicillamine methyl ester

Abstract

Reaction of oxorhenium(V) gluconate with D-penicillamine methyl ester (methyl 3-sulfanylvalinate) yielded three neutral 1∶2 complexes. For two complexes (1 and 2) the ¹H NMR spectrum in (CD₃)₂SO shows the presence of a deprotonated and a neutral nitrogen donor group in the ReO(NS)₂ system which is an unusual co-ordination mode for bidentate N,S ligands. Complex 1, [ReO{SC(CH₃)₂CH(CO₂CH₃)NH₂}{SC(CH₃)₂CH(CO₂CH₃)NH}], possibly containing in non-co-ordinating solvents an ester oxygen co-ordinated trans to the Re[double bond, length half m-dash]O group, is able to bind a water molecule trans to the oxo core to give species 2. In aqueous solution the mixed-ligand complex [ReO{SC(CH₃)₂CH(CO₂CH₃)NH₂}{SC(CH₃)₂CH(CO₂)NH₂}] 3 was unexpectedly formed out of 1 and 2. It contains bidentate D-penicillamine methyl ester and tridentate D-penicillamine in a co-ordination geometry similar to that of the known D-penicillamine complex [ReO{SC(CH₃)₂CH(CO₂H)NH₂}{SC(CH₃)₂CH(CO₂)NH₂}] 4. Complexes 3 and 4 were structurally characterized by X-ray diffraction.

References

1. B. Johannsen and H. Spies, Top. Curr. Chem., 1996, 176, 77.
2. L. A. Epps, H. D. Burns, S. Z. Lever, H. W. Goldfarb and H. N. Wagner, jun., Appl. Radiat. Isot., 1987, 38, 661.
3. D. S. Edwards, E. H. Cheesman, M. W. Watson, L. J. Maheu, S. A. Nguyen, L. Dimitre, T. Nason, A. D. Watson and R. Walovitch, in Technetium and rhenium in chemistry and nuclear medicine, eds. M. Nicolini, G. Bandoli and U. Mazzi, Cortina International, Verona, Raven Press, New York, 1990, p. 433.
4. L. G. Marzilli, M. G. Banaszcyk, L. Hansen, Z. Kuklenyik, R. Cini and A. Taylor, jun., Inorg. Chem., 1994, 33, 4850.
5. S. Kirsch, B. Noll, D. Scheller, K. Klostermann, P. Leibnitz, H. Spies and B. Johannsen, Annual Report of the Institute of Bioinorganic and Radiopharmaceutical Chemistry, Rossendorf, 1995, pp. 110–114.
6. L. Hansen, M. Lipowska, A. Taylor, jun. and L. G. Marzilli, Inorg. Chem., 1995, 34, 3579.
7. B. Johannsen, R. Syhre, H. Spies and R. Münze, J. Nucl. Med., 1978, 19, 816.
8. K. J. Franklin, H. E. Howard-Lock and C. J. L. Lock, Inorg. Chem., 1982, 21, 1941.
9. A. Marchi, R. Rossi and L. Marvelli, Inorg. Chem., 1993, 32, 4673.
10. A. Wang and R. Liu, Nucl. Med. Biol., 1995, 22, 937.
11. J. Bonnyman, Nucl. Med. Biol., 1995, 22, 943.
12. S. Mansur, M. Jehangir, S. Stathaki, M. Papadopoulos, S. Mastrostamatis and E. Chiotellis, Nucl. Med. Biol., 1993, 20, 819.
13. L. Hansen, X. Xu, K. T. Yue, Z. Kuklenyik, A. Taylor, jun. and L. G. Marzilli, Inorg. Chem., 1996, 35, 1958.
14. L. Hansen, X. Xu, K. T. Yue, A. Taylor, jun. and L. G. Marzilli, Inorg. Chem., 1996, 35, 2785.
15. B. Noll, T. Kniess, M. Friebe, H. Spies and B. Johannsen, Isot. Environ. Health Stud., 1996, 32, 21.
16. C. K. Johnson, ORTEP, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, TN, 1976.
17. M. Karplus, J. Am. Chem. Soc., 1963, 85, 2870; Karplus equation: J(θ)=A cos²θ+B cos θ+C where θ is the dihedral angle, the values A, B, C depend on the precise system under investigation and in particular are sensitive to the electronegativity of the substituents on the carbons etc.
18. T. Krueger, unpublished work.
19. N. Walker and D. Stuart, DIFABS, Acta Crystallogr., Sect. A, 1983, 39, 158; G. Reck and R. G. Kretschmer, CELLGRAF, a program for representation of organic and inorganic crystal structures, Analytisches Zentrum Berlin 1989/1991; CAD4 Operations Manual, Enraf-Nonius, Delft, 1977; C. K. Fair, MOLEN, An Interactive Intelligent System for Crystal Structure Analysis, User Manual, Enraf-Nonius, Delft, 1990; W. H. Zachariasen, Acta Crystallogr., 1963, 16, 1139; P. Main, S. J. Fiske, S. E. Hull, L. Lessinger, G. Germain, J. P. DeClerq and M. M. Woolfson, MULTAN 80, University of York, 1980.
20. M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez and J. A. Pople, GAUSSIAN 94, Revision B.2, Gaussian Inc., Pittsburgh, PA, 1995.
21. Amsterdam Density Functional (ADF): E. J. Baerends, D. E. Ellis and P. Ros, Chem. Phys., 1973, 2, 42; E. J. Baerends and P. Ros, Chem. Phys., 1973, 2, 51; Int. J. Quantum Chem., 1978, 512, 169; P. M. Boerrigter, G. te Velde and E. J. Baerends, Int. J. Quantum Chem., 1988, 33, 87; G. te Velde and E. J. Baerends, J. Comput. Phys., 1992, 99, 84.