Lanthanide organometallic chemistry based on the porphyrinogen skeleton: acetylene and ethylene bridging praseodymium and neodymium η⁵:η¹:η⁵:η¹-bonded to meso-octaethylporphyrinogen

Abstract

The reaction of meso-octaethylporphyrinogen–lanthanide complexes, [{(η⁵∶η¹∶η⁵∶η¹-Et₈N₄)M}Na(thf)₂] [M = Pr, Nd], with NaC₁₀H₈ in an ethylene or acetylene atmosphere leads to the isolation of dimeric species, where the metals are bridged by the [C₂H₄]^2– and [C₂]^2– anions.

References

1. (a) D. Jacoby, C. Floriani, A. Chiesi-Villa and C. Rizzoli, J. Am. Chem. Soc., 1993, 115, 3595; (b) D. Jacoby, S. Isoz, C. Floriani, A. Chiesi-Villa and C. Rizzoli, J. Am. Chem. Soc., 1995, 117, 2793; (c) C. Floriani, in Stereoselective Reactions of Metal-Activated Molecules, ed. H. Werner and J. Sundermeyer, Vieweg, Wiesbaden, 1995, pp. 97–106; (d) D. Jacoby, S. Isoz, C. Floriani, K. Schenk, A. Chiesi-Villa and C. Rizzoli, Organometallics, 1995, 14, 4816; (e) S. Isoz, C. Floriani, K. Schenk, A. Chiesi-Villa and C. Rizzoli, Organometallics, 1996, 15, 337; (f) E. Solari, F. Musso, C. Floriani, A. Chiesi-Villa and C. Rizzoli, J. Chem. Soc., Dalton Trans., 1994, 2015; (g) D. Jacoby, S. Isoz, C. Floriani, A. Chiesi-Villa and C. Rizzoli, J. Am. Chem. Soc., 1995, 117, 2805; (h) C. Floriani, Pure Appl. Chem., 1996, 68, 1; (i) R. Crescenzi, E. Solari, C. Floriani, N. Re, A. Chiesi-Villa and C. Rizzoli, Organometallics, 1999, 18, 606.
2. (a) S. De Angelis, E. Solari, C. Floriani, A. Chiesi-Villa and C. Rizzoli, Angew. Chem., Int. Ed. Engl., 1995, 34, 1092; (b) S. De Angelis, E. Solari, C. Floriani, A. Chiesi-Villa and C. Rizzoli, Organometallics, 1995, 14, 4505; (c) G. Solari, E. Solari, C. Floriani, A. Chiesi-Villa and C. Rizzoli, Organometallics, 1997, 16, 508; (d) C. Floriani, E. Solari, G. Solari, A. Chiesi-Villa and C. Rizzoli, Angew. Chem., Int. Ed., 1998, 37, 2245; (e) L. Bonomo, O. Dandin, E. Solari, C. Floriani and R. Scopelliti, Angew. Chem. Int. Ed., 1999, 38, 913.
3. G. B. Deacon and Q. Shen, J. Organomet. Chem., 1996, 506, 1 and references therein.
4. (a) W. J. Evans, D. K. Drummond, L. R. Chamberlain, R. J. Doedens, S. G. Bott, H. Zhang and J. L. Atwood, J. Am. Chem. Soc., 1988, 110, 4983; (b) W. J. Evans and D. K. Drummond, J. Am. Chem. Soc., 1988, 110, 2772; (c) W. J. Evans and D. K. Drummond, J. Am. Chem. Soc., 1989, 111, 3329; (d) W. J. Evans, J. T. Leman, J. W. Ziller and S. I. Khan, Inorg. Chem., 1996, 35, 4283; (e) W. J. Evans, T. A. Ulibarri, L. R. Chamberlain, J. W. Ziller and D. Alvarez, Jr., Organometallics, 1990, 9, 2124; (f) W. J. Evans and D. K. Drummond, Organometallics, 1988, 7, 797; (g) W. J. Evans, R. A. Keyer, G. W. Rabe, D. K. Drummond and J. W. Ziller, Organometallics, 1993, 12, 4664.
5. (a) R. D. Ernst and T. J. Marks, J. Organomet. Chem., 1987, 318, 29; (b) R. D. Ernst, J. Organomet. Chem., 1990, 392, 51; (c) R. D. Rogers and L. M. Rogers, J. Organomet. Chem., 1990, 380, 51; 1991, 416, 201; 1992, 442, 83; 1992, 442, 225; (d) T. J. Marks and R. D. Ernst in Comprehensive Organometallic Chemistry, ed. G. Wilkinson, F. G. A. Stone and E. W. Abel, Pergamon, Oxford, 1982 vol.III, ch.21; (e) F. T. Edelmann, in Comprehensive Organometallic Chemistry II, ed. E. W. Abel, F. G. A. Stone and G. Wilkinson, Pergamon, Oxford, 1995, vol. 4, ch. 2; (f) M. Ephtrikhine, Chem. Rev., 1997, 97, 2193; (g) H. Schumann, J. A. Meese-Marktscheffel and L. Esser, Chem. Rev., 1995, 95, 865.
6. Samarium has been complexed to the same kind of macrocycle in: J. L. Song and S. Gambarotta, Angew. Chem.. Int. Ed. Engl., 1995, 34, 2141; J. Jubb and S. Gambarotta, J. Am. Chem. Soc., 1994, 116, 4477.
7. (a) D. J. Schwartz, G. E. Ball and R. A. Andersen, J. Am. Chem. Soc., 1995, 117, 6027; (b) D. J. Schwartz and R. A. Andersen, Organometallics, 1995, 14, 4308.
8. For a very interesting approach in the field see: M. C. Cassani, D. J. Duncalf and M. F. Lappert, J. Am. Chem. Soc., 1998, 120, 12958.
9. E. Campazzi, E. Solari, C. Floriani and R. Scopelliti, Chem. Commun., 1998, 2603.
10. W. J. Evans, T. A. Ulibarri and J. W. Ziller, J. Am. Chem. Soc., 1990, 112, 219; 2314 and references therein.
11. (a) W. J. Evans, G. W. Rabe and J. W. Ziller, J. Organomet. Chem., 1994, 483, 21; (b) W. J. Evans, R. A. Keyer and J. W. Ziller, Organometallics, 1993, 12, 2618.