Heterolytic dihydrogen activation in an iridium complex with a pendant basic group

Abstract

Experimental and theoretical studies show that H₂ reacts with an Ir phosphine complex having a basic pendant amino group to give either an H₂ or an Ir–H···H–N hydrogen-bonded hydride complex, depending on the basicity of the phosphine ligands.

References

1. D. M. Heinekey and W. J. Oldham Jr., Chem. Rev., 1993, 93, 913.
2. R. H. Crabtree, Angew. Chem., Int. Ed. Engl., 1992, 32, 789.
3. P. J. Brothers, Prog. Inorg. Chem., 1981, 28, 1.
4. J. Huhmann-Vincent, B. L. Scott and G. J. Kubas, J. Am. Chem. Soc., 1998, 120, 6808.
5. K. T. Smith, M. Tilset, R. Kuhlman and K. G. Caulton, J. Am. Chem. Soc., 1995, 117, 9473.
6. M. Schlaf, A. J. Lough, P. A. Maltby and R. H. Morris, Organometallics, 1996, 15, 2270.
7. B. P. Patel and R. H. Crabtree, J. Am. Chem. Soc., 1996, 118, 13105.
8. R. H. Crabtree, M. Lavin and L. Bonneviot, J. Am. Chem. Soc., 1986, 108, 4032.
9. A. Tolman, Chem Rev., 1977, 77, 313.
10. K. Gruet, D.-H. Lee and R. H. Crabtree, unpublished work.
11. R. H. Crabtree, P. E. M. Siegbahn, O. Eisenstein, A. L. Rheingold and T. F. Koetzle, Acc. Chem. Res., 1996, 29, 348; A. J. Lough and R. H. Morris, Inorg. Chem., 1995, 34, 1549.
12. Gaussian 94, Revision B.3, M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Kerth, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, 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 Inc, Pittsburgh PA, 1995.
13. A. D. Becke, J. Chem. Phys., 1993, 98, 5648.
14. J. P. Perdew and Y. Wang, Phys. Rev. B, 1992, 45, 13244.
15. P. J. Hay and W. R. Wadt, J. Chem. Phys., 1985, 82, 299.
16. W. R. Wadt and P. J. Hay, J. Chem. Phys., 1985, 82, 284.
17. A. Hölwarth, M. Böhme, S. Dapprich, A. W. Ehlers, A. Gobbi, V. Jonas, K. Köhler, R. Stegmann, A. Veldkamp and G. Feenking, Chem. Phys. Lett., 1993, 208, 237.
18. W. J. Hehre, R. Ditchfield and J. A. Pople, J. Chem. Phys., 1972, 56, 2257.
19. P. C. Harihan and J. A. Pople, Theor. Chim. Acta, 1973, 28, 213.
20. G. Jia and R. H. Morris, J. Am. Chem. Soc., 1991, 113, 875.