S7NH and S7NCH3 as Novel Chelating Ligands in [(η5-C5H5)2Ti] Complexes: Synthesis of Medium-Sized Sulfur–Nitrogen Rings by Ligand Transfer†
Dipl.-Chem. Klaus Bergemann
Institut für Anorganische und Analytische Chemie der Technischen Universität, Sekr. C 2, D-10623 Berlin (Germany), Telefax: Int. code + (30)3142-6519, e-mail: [email protected]
Search for more papers by this authorDr. Monika Kustos
Institut für Anorganische und Analytische Chemie der Technischen Universität, Sekr. C 2, D-10623 Berlin (Germany), Telefax: Int. code + (30)3142-6519, e-mail: [email protected]
Search for more papers by this authorDipl.-Chem. Per Krüger
Institut für Anorganische und Analytische Chemie der Technischen Universität, Sekr. C 2, D-10623 Berlin (Germany), Telefax: Int. code + (30)3142-6519, e-mail: [email protected]
Search for more papers by this authorCorresponding Author
Prof. Dr. Ralf Steudel
Institut für Anorganische und Analytische Chemie der Technischen Universität, Sekr. C 2, D-10623 Berlin (Germany), Telefax: Int. code + (30)3142-6519, e-mail: [email protected]
Institut für Anorganische und Analytische Chemie der Technischen Universität, Sekr. C 2, D-10623 Berlin (Germany), Telefax: Int. code + (30)3142-6519, e-mail: [email protected]Search for more papers by this authorDipl.-Chem. Klaus Bergemann
Institut für Anorganische und Analytische Chemie der Technischen Universität, Sekr. C 2, D-10623 Berlin (Germany), Telefax: Int. code + (30)3142-6519, e-mail: [email protected]
Search for more papers by this authorDr. Monika Kustos
Institut für Anorganische und Analytische Chemie der Technischen Universität, Sekr. C 2, D-10623 Berlin (Germany), Telefax: Int. code + (30)3142-6519, e-mail: [email protected]
Search for more papers by this authorDipl.-Chem. Per Krüger
Institut für Anorganische und Analytische Chemie der Technischen Universität, Sekr. C 2, D-10623 Berlin (Germany), Telefax: Int. code + (30)3142-6519, e-mail: [email protected]
Search for more papers by this authorCorresponding Author
Prof. Dr. Ralf Steudel
Institut für Anorganische und Analytische Chemie der Technischen Universität, Sekr. C 2, D-10623 Berlin (Germany), Telefax: Int. code + (30)3142-6519, e-mail: [email protected]
Institut für Anorganische und Analytische Chemie der Technischen Universität, Sekr. C 2, D-10623 Berlin (Germany), Telefax: Int. code + (30)3142-6519, e-mail: [email protected]Search for more papers by this authorSulfur Compounds, Part 185. This work was supported by the Deutsche Forschungsgemeinschaft. Part 184: Y. Drozdova, R. Steudel, Chem. Eur. J. 1995, 1, 193.
Graphical Abstract
The insertion of titanocene, prepared from the corresponding dicarbonyl complex, into SS bonds of S7NH and S7NMe affords the complexes 1 and 2, respectively, which are suitable as precursors for large SN rings. The treatment of 2 with SCl2 and S2Cl2 yields the imides S8NMe and S9NMe, respectively.
References
- 1(a) H. G. Heal, The Inorganic Heterocyclic Chemistry of Sulfur, Nitrogen and Phosphorus, Academic Press, London, 1980; (b) T. Chivers, in The Chemistry of Inorganic Homo-and Heterocycles, Vol. 2, (Eds.: I. Haiduc, D. B. Sowerby), Academic Press, London, 1987, p. 793; (c) T. Chivers, in Encyclopedia of Inorganic Chemistry, Vol. 7, (Ed.: R. B. King), Wiley, Chichester, 1994.
- 2 B. Krebs, M. Hein, M. Diehl, H. W. Roesky, Angew. Chem. 1978, 90, 825; Angew. Chem. Int. Ed. Engl. 1978, 17, 778.
- 3 R. Steudel, Top. Curr. Chem. 1982, 102, 149; R. Steudel, in The Chemistry of Inorganic Homo- and Heterocycles, Vol. 2, (Eds.: I. Haiduc, D. B. Sowerby), Academic Press, London, 1987, p. 737.
- 4(a) G. Müller, J. L. Peterson, J. Org. Chem. 1974, 111, 91; (b) U. Westphal, R. Steudel, Phosphorus Sulfur Silicon 1992, 65, 151.
- 5 A. Shaver, S. Morris, Inorg. Chem. 1991, 30, 1926; G. Facchinetti, C. Floriani, J. Chem. Soc. Dalton Trans. 1974, 2433.
- 6 The reaction of [Cp2Ti(CO)2] with S4N4 yielded [Cp2Ti(NSN)2S] and [Cp2Ti(NSN)SS]; C. M. Marcellus, R. T. Oakley, W. T. Pennigton, A. W. Cordes, Organometallics 1986, 5, 1395. Review on metal complexes with sulfur–nitrogen ligands: P. F. Kelly, J. D. Woolins, Polyhedron 1986, 5, 607.
- 7 Crystal structure analyses: 1: 0.45 × 0.25 × 0.1 mm, monoclinic, P21/n, Z = 4 a = 825.6(3), b = 1089.7(7), c = 1744(2)pm, β = 93.87(5)°, V = 1565(2) × 106 pm3, ρcalcd = 1.772(2) g cm−3, 2θmax = 55°, MoKα radiation, λ = 71.069 pm. ω-2θ scan, T = 298 K, 3960 measured, 3517 independent and 1545 observed reflections, criterium: I ≥ 2σ(I), no absorption correction, structure solved by direct method (program: SHELXS 86), refined versus F2 (program: SHELXL 93) with anisotropic temperature factors for all non-hydrogen atoms, positions of hydrogen atoms calculated, R = 0.0097 with 172 refinded parametes, residual electron density (max/min): 0.69/-0.66 e Å−3. 2: 0.3 × 0.4 × 0.15 mm, monoclinc, P21/n, Z = 4 a = 858.8(2), b = 1555.1(5), c = 1239.8(3) pm, β = 90.04(2)°, V = 1655.7(7) × 106 pm3, ρcalcd = 1.731 g cm−3, 2θmax = 55°, MoKα, λ = 71.069 pm, ω-2θ scan, T = 298 K, 4195 measured, 3041 independent and 2497 observed reflections with I≥2σ(I), μ = 1.35 mm−1, absorption correction (DIFABS) (Tmin/Tmax) 0.857/1.100, solved by direct method (SHELXS 86), refinement (SHELX 76) versus F2 with anisotropic temperature factors, hydrogen atoms calculated, free parameters 182, R = 0.057, Rw = 0.057, residual electron density (max/min): 0.522/-0.477 e Å−3. Further details on the crystal structure investigations are available on request from the Fachinformationszentrum Karlsruhe, D-76344 Eggenstein-Leopoldshafen (Germany), on quoting the depository numbers CSD-401514 (1) or CSD-401515 (2).
- 8Two C18-columns in line (l = 2 × 10 cm; 10μm and 5μm particle diameter), eluant: methanol. In the case of the isomeric complexes [Cp2Ti(μ-S2) (μ-S2)AsCH3] and [Cp2Ti(μ-S)(μ-S3)AsCH3] the retention times differ considerably; see B. Holz, Dissertation, Technische Universität Berlin, 1991.
- 9 Simulation of the powder diffractogram with the program LAZY PULVERIX. Measurement in the angle range 2θ = 9–27° with a Siemens apparatus D5000. We thank Dipl.-Chem. U. Stege for this measurement.
- 10In free S7NH the N atom has a planar or nearly planar coordination: see H.-J. Hecht, R. Reinhardt, R. Steudel, H. Bradaczek, Z. Anorg. Allg. Chem. 1976, 426, 43. The structure of S7NCH3 is unknown.
- 11The same ring size occurs in [Cp2TiS8]: ref. [4b] and U. Westphal, Dissertation, Technische Universität Berlin, 1994.
- 12 D. Hohl, R. O. Jones, R. Car, M. Parrinello, J. Chem. Phys. 1988, 89, 6823.
- 13The torsion barrier at cumulated S–S bonds is about 27 (trans-barrier) or 32 (cis-barrier) kJ mol−1; see Y. Drozdova, K. Miaskiewicz, R. Steudel, Z. Naturforsch. Part B 1995, 50, 889.
- 14 Fquimolar amounts of 2 and SCl2 or S2Cl2, respectively, were allowed to react with each other at 20 °C in CS2. After removal of the solvent in vacuo 3 and 4 were extracted with n-pentane. Compounds 3 and 4 were obtained as yellow oils from the extracts, the HPLC analyses of which show small portions of homologous rings S8NCH3. MS (EI, 70 eV. 90 °C): B+ 160 (S3), M+ 285 (S8NCH3), and 317 (S9NCH3), respectively.
- 15Column: C18, 10 μm; eluant: methanol. For HPLC analysis of SN compounds see R. Steudel, D. Rosenbauer, J. Chromatogr. 1981, 216, 399.
- 16
R. Steudel, in
The Chemistry of Inorganic Ring Systems, (Ed.
R. Steudel),
Elsevier, Amsterdam, 1992, p. 233.
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