Two different types of 2-thienyl bridge in dinuclear manganese and rhenium compounds

Abstract

Thermal and photochemical reactions of diphenyl-2-thienylphosphine (L) with [Mn₂(CO)₁₀] gave simple substitution products [Mn₂(CO)_10 – nL_n] 1 (n = 1) and 2 (n = 2) with ligand L co-ordinated through the phosphorus atom. Under forcing conditions (refluxing xylene) oxidative addition with P–C cleavage occurred to give the µ-2-thienyl complex [Mn₂(CO)₆(µ-PPh₂)(µ-η¹∶η⁵-C₄H₃S)] 3. Loss of CO and P–C bond cleavage do not occur so easily in the case of [Re₂(CO)₁₀]. UV Treatment of the rhenium carbonyl with L gave [Re₂(CO)₈(µ-P,S-Ph₂PC₄H₃S)] 4, in which the ligand L is bridging through the two heteroatoms. Oxidative addition occurs internally at about 180° in decane with rupture of a P–C bond to produce an isomer of 4, [Re₂(CO)₈(µ-PPh₂)(µ-η¹∶η¹-C,S-C₄H₃S)] 5. Crystal structures revealed a novel form of bridging of L co-ordinated through P and S in 4 and two different modes of 2-thienyl bridge (µ-η²∶η⁵ and µ-η¹∶η¹-C,S) in 3 and 5 respectively. With the previously known µ-η¹∶η²-bridging form of thienyl, these new compounds 3 and 5 provide three distinct type of thienyl bridge. The type of bridge which is formed depends upon the electronic requirements of the metal atoms and the span between them.

References

1. (a) See the recent collection of papers appearing in Polyhedron, 1997, 16, 3071; (b) T. B. Rauschfuss, Prog. Inorg. Chem., 1991, 39, 259; (c) R. J. Angelici, Coord. Chem. Rev., 1990, 105, 61; (d) C. Bianchini and A. Meli, Acc. Chem. Res., 1998, 31, 109; J. Chem. Soc., Dalton Trans., 1996, 801; (e) J. J. Garcia, B. E. Mann, H. Adams, N. A. Bailey and P. M. Maitlis, J. Am. Chem. Soc., 1995, 117, 2179.
2. M.-G. Choi and R. J. Angelici, J. Am. Chem. Soc., 1989, 111, 8753.
3. M. F. Bailey and L. F. Dahl, Inorg. Chem., 1965, 4, 1306.
4. R. A. Sanchez-Delgado, R. L. Marquez-Silva, J. Puga, A. Tiripicchio and M. Tiripicchio Camellini, J. Organomet. Chem., 1986, 316, C35.
5. J. Chen and R. J. Angelici, Organometallics, 1989, 8, 2277.
6. R. Cordore, W. D. Harman and H. Taube, J. Am. Chem. Soc., 1989, 111, 5969.
7. S. Harris, Organometallics, 1994, 13, 2628.
8. M.-G. Choi and R. J. Angelici, Organometallics, 1992, 11, 3328.
9. W. D. Jones, Polyhedron, 1997, 16, 3115; I. E. Buys, L. D. Field, T. W. Hambley and A. E. D. McQueen, J. Chem. Soc., Chem. Commun., 1994, 557; M. Paneque, S. Taboada and E. Carmona, Organometallics, 1996, 15, 2678; W. D. Jones, R. M. Chin, T. W. Crane and D. M. Baruch, Organometallics, 1994, 13, 4448.
10. D. G. Dick and D. W. Stephan, Can. J. Chem., 1986, 64, 1870; A. R. Sanger, Can. J. Chem., 1984, 62, 2168; A. Varchrey and G. M. Gray, Inorg. Chim. Acta, 1988, 148, 215; U. Bodensiek, H. Vahrenkamp, G. Rheinwald and H. Stoeckli-Evans, J. Organomet. Chem., 1995, 488, 85.
11. A. J. Deeming, S. N. Jayasuriya, A. J. Arce and Y. De Sanctis, Organometallics, 1996, 15, 786.
12. U. Koelle, J. Organomet. Chem., 1978, 155, 53.
13. T. A. Waldbach, P. H. van Rooyen and S. Lotz, Angew. Chem., Int. Ed. Engl., 1993, 32, 710; S. Lotz, P. H. van Rooyen and R. Meyer, Adv. Organomet. Chem., 1995, 37, 219.
14. A. J. Deeming, M. K. Shinhmar and M. B. Smith, unpublished results.
15. R. D. Adams and X. Qu, Organometallics, 1995, 14, 2238.
16. A. J. Arce, A. J. Deeming, Y. De Sanctis, D. M. Speel and A. Di Trapani, J. Organomet. Chem., in the press.
17. Y. Xie, S. C. Ng, B.-M. Wu, F. Xue, T. C. Mak and T. S. A. Hor, J. Organomet. Chem., 1997, 531, 175; M. Paneque, S. Taboada and E. Carmona, Organometallics, 1996, 15, 2678; K. Onitsuka, K. Murakami, K. Matsukawa, K. Somogashira, T. Adachi and T. Yoshida, J. Organomet. Chem., 1995, 490, 117; M. H. Chisholm, S. T. Haubrich, J. D. Martin and W. E. Streib, J. Chem. Soc., Chem. Commun., 1994, 683.
18. A. J. Arce, J. Manzur, M. Marquez, Y. De Sanctis and A. J. Deeming, J. Organomet. Chem., 1991, 412, 177; M. W. Day, K. I. Hardcastle, A. J. Deeming, A. J. Arce and Y. De Sanctis, Organometallics, 1990, 9, 6.
19. D. W. Allen, J. R. Charlton and B. G. Hutley, Phosphorus, 1976, 6, 191.
20. G. M. Sheldrick, SHELXTL PLUS, University of Göttingen, released by Nicolet Instruments Corporation, 1987.
21. G. M. Sheldrick, SHELXL 93, Program for refinement of crystal structures, University of Göttingen, 1993.