Dinuclear ruthenium(II) carbonyl complexes bridged by a C(O)CH₂C₅H₃NCH₂ group: synthesis, characterization and crystal structures

Abstract

The reaction of [Ru₃(CO)₁₂] with 2,6-bis(chloromethyl)pyridine (ClCH₂C₅H₃NCH₂Cl) gave the scarcely soluble complex 1, [Ru₂Cl₂{C(O)CH₂C₅H₃NCH₂}(CO)₄]. Further reactions of 1 with MeOH and PPh₃ under appropriate conditions afforded organic-soluble complexes [Ru₂(µ-Cl){µ-C(O)CH₂C₅H₃NCH₂-C,N,C ′}Cl(CO)₄(MeOH)₂] 2 and [Ru₂(µ-Cl){µ-C(O)CH₂C₅H₃NCH₂-C,N,C ′}Cl(CO)_n(PPh₃)_m] (n = 4, m = 1 3; n = 3, m = 2 4), respectively. Complexes 2–4 were characterized by ¹H, ¹³C and ³¹P (for 3 and 4) NMR spectroscopy and by single-crystal structure determinations. These complexes are dinuclear and two Ru atoms are doubly connected by a chlorine atom and a C(O)CH₂C₅H₃NCH₂ group. Each of the metal atoms in 2 has a distorted octahedral co-ordination, while in 3 and 4 one metal atom adopts a distorted octahedral geometry and the other pseudo-octahedral; the latter geometry is completed by a Ru  · · ·  Cl secondary bonding interaction [2.855(2) in 3; 2.941(2) Å in 4].

References

1. (a) K. Higashimura and Y. Nakamura, J. Chem. Soc., Dalton Trans., 1993, 3075; (b) Y. Nakamura and N. Shinkawa, Rhodium Express, 1994, 6, 14; (c) N. Shinkawa, A. Sato, J. Shinya, Y. Nakamura and S. Okeya, Bull. Chem. Soc. Jpn., 1995, 68, 183; (d) K. Yamasaki, H. Saito, M. Tadokoro, K. Matsumoto, S. Miyajima and Y. Nakamura, Bull. Chem. Soc. Jpn, 1997, 70, 2155.
2. For recent reviews, see E. Sappa in Comprehensive Organometallic Chemistry, eds. E. W. Abel, F. G. A. Stone and G. Wilkinson, Pergamon, Oxford, 1995, vol. 7, ch. 14, pp. 803–834; M. I. Bruce, M. P. Cifuentes and M. G. Humphrey, Polyhedron, 1991, 10, 277.
3. M. I. Bruce, M. G. Humphrey, M. R. Snow, E. R. T. Tiekink and R. C. Wallis, J. Organomet. Chem., 1986, 314, 311.
4. A. Eisenstadt, C. M. Giandomenico, M. F. Frederick and R. M. Laine, Organometallics, 1985, 4, 2033.
5. G. A. Foulds, B. F. G. Johnson and J. Lewis, J. Organomet. Chem., 1985, 296, 147.
6. G. A. Foulds, B. F. G. Johnson and J. Lewis, J. Organomet. Chem., 1985, 294, 123.
7. P. A. Andreu, J. A. Cabeza, V. Riera, Y. Jeannin and D. Migual, J. Chem. Soc., Dalton Trans., 1990, 2201.
8. A. J. Deeming, K. I. Hardcastle and M. Karim, Inorg. Chem., 1992, 31, 4792.
9. A. Maisonnet, J. P. Farr, M. M. Olmstead, C. T. Hunt and A. L. Balch, Inorg. Chem., 1982, 21, 3961; N. Lugan, G. Lavigne and J.-J. Bonnet, Inorg. Chem., 1987, 26, 585.
10. M. Shimizu, Y. Nakamura and M. Tadokoro, Polyhedron, 1997, 16, 577.
11. M. Shimizu, Y. Nakamura and M. Tadokoro, Chem. Lett., 1996, 773.
12. W. R. Busing and H. A. Levy, Acta Crystallogr., 1957, 10, 180.
13. N. Walker and D. Stuart, Acta Crystallogr., Sect. A, 1983, 39, 158.
14. P. T. Beurskens, G. Admiraal, G. Beurskens, W. P. Bosman, R. de Gelder, R. Israel and J. M. M. Smits, DIRDIF 94, The DIRDIF 94 Program System, Technical Report of the Crystallography Laboratory, University of Nijmegen, 1994.
15. P. T. Beurskens, G. Admiraal, G. Beurskens, W. P. Bosman, S. Garcia-Granda, R. O. Gould, J. M. M. Smits and C. Smykalla, PATTY, The DIRDIF Program System, Technical Report of the Crystallography Laboratory, University of Nijmegen, 1992.
16. H.-F. Fan, SAPI 91, Structure Analysis Programs with Intelligent Control, Rigaku Corporation, Tokyo, 1991.
17. A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, M. C. Burla, G. Polidori and M. Camalli, SIR 92, J. Appl. Crystallogr., 1994, 27, 435.
18. TEXSAN, Crystal Structure Analysis Package, Molecular Structure Corporation, Houston, TX, 1985 and 1992.
19. N. W. Alcock, Adv. Inorg. Radiochem., 1972, 15, 1.
20. R. J. Kulawiec and R. H. Crabtree, Coord. Chem. Rev., 1990, 99, 89.
21. A. G. Orpen, L. Brammer, F. H. Allen, O. Kennard, D. G. Watson and R. Taylor, in International Tables for Crystallography, ed. A. J. C. Wilson, Kluwer, Dordrecht, 1992, vol. C, ch. 9, p. 774.
22. M. F. Richardson, G. Wulfsberg, R. Marlow, S. Zaghonni, D. McCorkle, K. Shadid, J. Gagliardi, jun. and B. Farris, Inorg. Chem., 1993, 32, 1913.
23. M. P. Garcia, M. V. Jiménez, A. Cuesta, C. Siurana, L. A. Oro, F. J. Lahoz, J. A. López, M. P. Catalán, A. Tiripicchio and M. Lanfranchi, Organometallics, 1997, 16, 1026.