Synthesis and characterization of dinuclear complexes of 3,3′,4,4′-tetraminobiphenyl with tetramminoruthenium and bis(bipyridine)ruthenium residues and their two- and four-electron oxidized products including a ZINDO study of orbital mixing as a function of ligand oxidation state †

Abstract

This paper reports the synthesis, characterisation and reactivity of new complexes of ruthenium, the symmetric dinuclear complex of ruthenium tetrammine [(Ru(NH₃)₄)₂(catH₄·catH₄)](PF₆)₄ and the asymmetric dinuclear complex of ruthenium bis(bipyridine) and ruthenium tetrammine [Ru(NH₃)₄(catH₄·catH₄)Ru(bpy)₂](PF₆)₄ where (catH₄·catH₄) represents the bridging ligand 3,3′,4,4′-tetraminobiphenyl. These complexes can be oxidized to the two-electron oxidized ligand mixed valence (qH₂·catH₄) species and the four-electron oxidized ligand (qH₂·qH₂) species. Further oxidation yields a range of Ru(III) species. These complexes were studied by proton NMR, UV–VIS spectra, cyclic voltammetry and ZINDO/1 and ZINDO/S calculations.

References

1. (a) R. A. Metcalfe and A. B. P. Lever, Inorg. Chem., 1997, 36, 4762; (b) R. A. Metcalfe, E. S. Dodsworth, S. S. Fielder, D. J. Stufkens, A. B. P. Lever and W. J. Pietro, Inorg. Chem., 1996, 35, 7741; (c) R. A. Metcalfe, Ph.D. Thesis, York University, Canada, 1988.
2. C. J. da Cunha, S. S. Fielder, D. V. Stynes, H. Masui, P. R. Auburn and A. B. P. Lever, Inorg. Chim. Acta., 1996, 242, 293.
3. R. A. Metcalfe, E. S. Dodsworth, W. J. Pietro, A. B. P. Lever and D. J. Stufkens, Inorg. Chem., 1993, 32, 3581.
4. P. R. Auburn and A. B. P. Lever, Inorg. Chem., 1990, 29, 2551.
5. (a) H. Masui, A. B. P. Lever and P. R. Auburn, Inorg. Chem., 1991, 30, 2402; (b) H. Masui, A. B. P. Lever and E. S. Dodsworth, Inorg. Chem., 1993, 32, 258; (c) H. Masui, Ph.D. Thesis, York University, Canada, 1994; (d) H. Masui, A. L. Freda and A. B. P. Lever, Inorg. Chem., submitted; (e) C. J. da Cunha, E. S. Dodsworth, M. A. Monteiro and A. B. P. Lever, Inorg. Chem., 1999, 38 in the press.
6. P. Belser, A. von Zelewsky and M. Zehnder, Inorg. Chem., 1981, 20, 3098; H. Y. Cheng and S. M. Peng, Inorg. Chim. Acta, 1990, 169, 23; E. H. Cutin, N. E. Katz, P. A. M. Williams and P. J. Aymonino, Transition Met. Chem., 1991, 16, 155; S. Nemeth and L. I. Simandi, Inorg. Chem., 1994, 33, 5964; G. Ricciardi, A. Rosa, G. Morelli and F. Lelj, Polyhedron, 1991, 10, 955; O. Carugo, K. Djinovic and C. B. Castellani, J. Chem. Soc., Dalton Trans., 1991, 1551; J. Rall, A. F. Stange, K. Hübler and W. Kaim, Angew. Chem., Int. Ed., 1998, 37, 2681; T. Jüstel, J. Bendix, N. Metzler, T. Weyhermüller, B. Nuber and K. Wieghardt, Inorg. Chem., 1998, 37, 35; S.-M. Peng, K. Peters, E. M. Peters and A. Simon, Inorg. Chim. Acta, 1985, 101, L35; S. Peng, C. Chen, D. Liaw, C. Chen and Y. Wang, Inorg. Chim. Acta, 1985, 101, L31; L. I. Simandi and S. Nemeth, Inorg. Chim. Acta, 1998, 270, 326.
7. J. F. Joulie, E. Schatz, M. D. Ward, F. Weber and L. J. Yellowlees, J. Chem. Soc., Dalton Trans., 1994, 799; S. Bruni, F. Cariati, A. Dei and D. Gatteschi, Inorg. Chim. Acta, 1991, 186, 157; A. Dei, D. Gatteschi and L. Pardi, Inorg. Chem., 1990, 29, 1442; M. D. Ward, Inorg. Chem., 1996, 35, 1712; F. Heinze, S. Mann, G. Huttner and L. Zsolnai, Chem. Ber., 1996, 129, 1115; A. Dei, D. Gatteschi, L. Pardi and U. Russo, Inorg. Chem., 1991, 30, 2589; A. Dei, D. Gatteschi and L. Pardi, Inorg. Chim. Acta, 1991, 189, 125; M. A. Calvo, A. M. M. Lanfredi, L. A. Oro, M. T. Pinillos, C. Tejel, A. Tiripicchio and F. Ugozzoli, Inorg. Chem., 1993, 32, 1147; S. Cueto, H. P. Straumann, P. Rys, W. Petter, V. Gramlich and F. S. Rys, Acta Crystallogr., Sect. C, 1992, 48, 458; A. Elduque, Y. Garces, L. A. Oro, M. T. Pinillos, A. Tiripicchio and F. Ugozzoli, J. Chem. Soc., Dalton Trans., 1996, 2155; R. F. Johnston, P. K. Sengupta, M. B. Ossain, R. Vanderhelm, W. Y. Jeong and R. A. Holwerda, Acta Crystallogr., Sect. C, 1990, 46, 1796; A. Tiripicchio, Inorg. Chem., 1993, 32, 1147; M. X. Zhang, Z. L. Liu, L. Yang and Y. C. Liu, J. Chem. Soc., Chem. Commun., 1991, 1054; J. Zubieta, J. Chem. Soc., Chem. Commun., 1988, 1017; T. E. Keyes, R. J. Forster, P. M. Jayaweera, C. G. Coates, J. J. McGarvey and J. G. Vos, Inorg. Chem., 1998, 37, 5925.
8. (a) W. P. Anderson, T. Cundari, R. S. Drago and M. C. Zerner, Inorg. Chem., 1989, 29, 1; (b) W. P. Anderson, T. Cundari and M. C. Zerner, Int. J. Quantum Chem., 1991, 39, 31; (c) W. P. Anderson, W. D. Edwards and M. C. Zerner, Inorg. Chem., 1986, 25, 2728; (d) A. D. Bacon and M. C. Zerner, Theor. Chim. Acta, 1979, 53, 21; (e) M. C. Zerner, Metal–Ligand Interactions, Kluwer Academic Publishers, Dordrecht, 1996, p. 493; (f) M. C. Zerner, G. H. Loew, R. F. Kirchner and U. T. Mueller-Westerhoff, J. Am. Chem. Soc., 1980, 102, 589; (g) J. C. Culberson, P. Knappe, N. Rösch and M. C. Zerner, Theor. Chim. Acta, 1987, 71, 21; (h) J. Ridley and M. C. Zerner, Theor. Chim. Acta, 1973, 32, 111; (i) J. Ridley and M. C. Zerner, Theor. Chim. Acta, 1976, 42, 223.
9. S. I. Gorelsky, E. S. Dodsworth, A. B. P. Lever and A. Vlcek, Coord. Chem. Rev., 1998, 174, 469.
10. Y. K. Shin, B. S. Brunschwig, C. Creutz, M. D. Newton and N. Sutin, J. Phys. Chem., 1996, 100, 1104 and references therein K. J. Lachance-Galang, P. E. Doan, M. J. Clarke, U. Rao, A. Yamano and B. M. Hoffman, J. Am. Chem. Soc., 1995, 117, 3529; L. T. Zhang and M. Ondrechen, Inorg. Chim. Acta, 1994, 226, 43; O. V. Sizova, V. I. Baranosvskii, N. V. Ivanova and A. B. Nikol'skii, Russ. J. Gen. Chem., 1997, 67, 1667; O. V. Sizova, V. I. Baranovski, N. V. Ivanova and A. I. Panin, Int. J. Quantum Chem., 1997, 65, 183; O. V. Sizova, V. I. Baranovskii, N. V. Ivanova and A. I. Panin, Russ. J. Coord. Chem., 1997, 23, 197; O. V. Sizova, N. V. Ivanova and A. B. Nikolskii, Zh. Obshch. Khim., 1997, 67, 26; O. V. Sizova, V. I. Baranovski, N. V. Ivanova and A. I. Panin, Int. J. Quantum Chem., 1997, 65, 183; O. V. Sizova, V. I. Baranovskii, N. V. Ivanova and A. I. Panin, Russ. J. Coord. Chem., 1997, 23, 197; O. V. Sizova, N. V. Ivanova, A. Y. Ershov, A. B. Nikolskii and I. V. Rogachevskii, Zh. Obshch. Khim., 1997, 67, 1409; O. V. Sizova, N. V. Ivanova and A. B. Nikolskii, Zh. Obshch. Khim., 1997, 67, 26; O. V. Sizova, A. I. Panin, N. V. Ivanova and V. I. Baranovskii, J. Struct. Chem., 1997, 38, 366; K. Shin, D. J. Szalda, B. S. Brunschwig, C. Creutz and N. Sutin, Inorg. Chem., 1997, 36, 3190; J. Yang, D. Seneviratne, G. Arbatin, A. M. Andersson and J. C. Curtis, J. Am. Chem. Soc., 1997, 119, 5329; A. Broo and P. Lincoln, Inorg. Chem., 1997, 36, 2544; H. Rensmo, S. Lunell and H. Siegbahn, J. Photochem. Photobiol. A: Chem., 1998, 114, 117; O. V. Sizova, V. I. Baranovskii, A. I. Panin, N. V. Ivanova and A. B. Nikolskii, Zh. Obshch. Khim., 1997, 67, 1611; O. V. Sizova, I. Panin, V. I. Baranovskii, A. B. Nikolskii and N. V. Ivanova, Zh. Obshch. Khim., 1997, 67, 1761.
11. See, for example: (a) S. Ernst, V. Kasack and W. Kaim, Inorg. Chem., 1988, 27, 1146; (b) S. Joss, H. Reust and A. Ludi, J. Am. Chem. Soc., 1981, 103, 981; (c) S. Joss, H. B. Burgi and A. Ludi, Inorg. Chem., 1985, 24, 949; (d) S. Joss, K. M. Hasselbach, H. B. Bürgi, R. Wordel, F. E. Wagner and A. Ludi, Inorg. Chem., 1989, 28, 1815; (e) J. E. B. Johnson, C. Degroff and R. R. Ruminski, Inorg. Chim. Acta, 1991, 187, 7380; (f) M. A. S. Aquino, F. L. Lee, E. J. Gabe, C. Bensimon, J. E. Greedan and R. J. Crutchley, J. Am. Chem. Soc., 1992, 114, 5130; (g) W. Bruns, W. Kaim, E. Waldhor and M. Krejcik, J. Chem. Soc., Chem. Commun., 1993, 1868; (h) C. Creutz, M. D. Newton and N. Sutin, J. Photochem. Photobiol. A, 1994, 82, 47; (i) H. Y. Huang, W. J. Chen, C. C. Yang and A. Yeh, Inorg. Chem., 1991, 30, 1862; (j) V. Kasack, W. Kaim, H. Binder, J. Jordanov and E. Roth, Inorg. Chem., 1995, 34, 1924; (k) J. A. Roberts and J. T. Hupp, Inorg. Chem., 1992, 31, 157; (l) M. D. Ward, Chem. Soc. Rev., 1995, 24, 121; (m) A. E. Almaraz, L. A. Gentil, L. M. Baraldo and J. A. Olabe, Inorg. Chem., 1997, 36, 1517; (n) J. F. Endicott, M. A. Watzky, X. Q. Song and T. Buranda, Coord. Chem. Rev., 1997, 159, 295; (o) F. Salaymeh, S. Berhane, R. Yusof, R. de la Rosa, E. Y. Fung, R. Matamoros, K. W. Lau, Q. Zheng, E. M. Kober and J. C. Curtis, Inorg. Chem., 1993, 32, 3895.
12. D. D. Perrin, W. L. F. Armarego and D. R. Perrin, Purification of Laboratory Chemicals, Pergamon Press, Elmsford, New York, 2nd edn., 1980.
13. A. B. P. Lever, E. R. Milaeva and G. Speier, Phthalocyanines: Properties and Applications, eds. C. C. Leznoff and A. B. P. Lever, VCH, New York, 1995, vol. 3, p. 3.
14. S. I. Gorelsky and A. B. P. Lever, unpublished work.
15. K. Krogh-Jespersen, J. D. Westbrook, J. A. Potenza and H. J. Schugar, J. Am. Chem. Soc., 1987, 109, 7025.
16. A. Szabo and N. S. Ostlund, Modern Quantum Chemistry, Macmillan Publ. Co., New York, 1982.
17. X. Cheng, Q. Gao, R. D. Smith, E. E. Simanek, M. Mammen and G. M. Whitesides, J. Org. Chem., 1996, 61, 2204; J. Manna, J. A. Whiteford, P. J. Stang, D. C. Muddiman and R. D. Smith, J. Am. Chem. Soc., 1996, 118, 8731; G. J. Langley, E. Hecquet, I. P. Morris and D. G. Hamilton, Rapid Commun. Mass Spectrom., 1997, 11, 165; A. Marquis-Rigault, A. Dupont-Gervais, A. Van Dorsselaer and J.-M. Lehn, Chem. Eur. J., 1996, 2, 1395; D. P. Funeriu, J.-M. Lehn, G. Baum and D. Fenske, Chem. Eur. J., 1997, 3, 99; C. Moucheron, A. Kirsch-De Mesmaeker, A. Dupont-Gervais, E. Leize and A. Van Dorsselaer, J. Am. Chem. Soc., 1996, 118, 12834; B. C. Gilbert, N. W. J. Kamp, J. R. Lindsay Smith and J. Oakes, J. Chem. Soc., Perkin Trans. 2, 1998, 1841; W. Henderson, J. S. McIndoe, B. K. Nicholson and P. J. Dyson, J. Chem. Soc., Dalton Trans., 1998, 519; C. Jiang, W. Henderson, T. S. A. Hor, L. J. McCaffrey and Y. K. Yan, Chem. Commun., 1998, 2029; A. S. Batsanov, A. V. Churakov, M. A. M. Easson, L. J. Govenlock, J. A. K. Howard, J. M. Moloney and D. Parker, J. Chem. Soc., Dalton Trans., 1999, 323; M. J. Deery, O. W. Howarth and K. R. Jennings, J. Chem. Soc., Dalton Trans., 1997, 4783; G. Hopfgartner, C. Piguet and J. D. Henion, J. Am. Soc. Mass Spectrom., 1994, 5, 748; C. Piguet, G. Bernardelli and H. Hopfgartner, Chem. Rev., 1997, 97, 2005; K. A. Hirsch, S. R. Wilson and J. S. Moore, J. Am. Chem. Soc., 1997, 199, 10401.
18. I. K. Chu, T.-C. Lau and K. W. M. Siu, J. Mass Spectrom., 1998, 33, 811.
19. C. G. Kuehn and H. Taube, J. Am. Chem. Soc., 1976, 98, 689; B. P. Sullivan, D. J. Salmon and T. J. Meyer, Inorg. Chem., 1978, 17, 3334.
20. S. Diamond, Ph.D Thesis, Stanford University, 1975.
21. L. Vasconcellos, R. A. Metcalfe, H. Mirza and A. B. P. Lever, to be published.
22. J. K. M. Sanders and B. K. Hunter, Modern NMR Spectroscopy, A Guide for Chemists, Oxford University Press, New York, 1978; J. B. Lambert, H. F. Shurvell, D. Lightner and R. G. Crooks, Introduction to Organic Spectroscopy, Macmillan Publishing Company, New York, 1987; R. D. Foust and P. C. Ford, J. Am. Chem. Soc., 1972, 94, 5686; C. A. Stein and H. Taube, J. Am. Chem. Soc., 1978, 100, 336; H. Lehmann, K. J. Schenk, G. Chapuis and A. Ludi, J. Am. Chem. Soc., 1979, 101, 6197; I. P. Evans, G. W. Everett and A. M. Sargeson, J. Am. Chem. Soc., 1976, 98, 8041.
23. M. Maruyama, H. Matsuzawa and Y. Kaizu, Inorg. Chim. Acta, 1995, 237, 159; M. Bourgault, T. Renouard, B. Lognone, C. Mountassir and H. LeBozec, Can. J. Chem., 1997, 75, 318; L. S. Kelso, D. A. Reitsma and F. R. Keene, Inorg. Chem., 1996, 35, 5144.
24. J. K. M. Sanders and B. K. Hunter, Modern NMR Spectroscopy, A Guide for Chemists, Oxford University Press, New York, 1978; J. B. Lambert, H. F. Shurvell, D. Lightner and R. G. Crooks, Introduction to Organic Spectroscopy, Macmillan Publishing Company, New York, 1987.
25. R. R. Ruminski and J. D. Petersen, Inorg. Chem., 1982, 21, 3706.
26. C. Creutz, Prog. Inorg. Chem., 1983, 30, 1 and references therein.
27. A. B. P. Lever, Inorg. Chem., 1990, 29, 1271.
28. P. Bernhard, D. J. Bull, H. B. Burgi, P. Osvath, A. Raselli and A. M. Sargeson, Inorg. Chem., 1997, 36, 2804; M. J. Ridd and F. R. Keene, J. Am. Chem. Soc., 1981, 103, 5733; V. L. Goedkin and D. H. Busch, J. Am. Chem. Soc., 1972, 94, 7355; P. Bernhard, D. J. Bull, H. B. Burgi, P. Osvath, A. Raselli and A. M. Sargeson, Inorg. Chem., 1997, 36, 2804; E. Jandrasics, B. Kolp, J. A. Wolny and A. von Zelewsky, Inorg. Chim. Acta, 1998, 272, 153; J. C. Dabrowiak, F. V. Lovecchio and D. H. Busch, J. Am. Chem. Soc., 1972, 94, 5502; R. Arakawa, S. Mimura, G. Matsubayashi and T. Matsuo, Inorg. Chem., 1996, 35, 5725; M. A. Fox and M. T. Dulay, Chem. Rev., 1993, 93, 341; B. C. Lane, J. E. Lester and F. Basolo, Chem. Commun., 1971, 1618; D. F. Mahoney and J. K. Beattie, Inorg. Chem., 1973, 12, 2561; F. R. Keene, P. A. Lay, G. E. Sneddon and G. W. Whebell, Aust. J. Chem., 1993, 46, 1763; P. Berhard and F. C. Anson, Inorg. Chem., 1989, 28, 3272; P. A. Lay, G. M. McLaughlin and A. M. Sargeson, Aust. J. Chem., 1987, 40, 1267; F. R. Keene, Coord. Chem. Rev., 1999, 187, 121.
29. P. H. Rieger, Coord. Chem. Rev., 1994, 135/136, 203 and references therein A. R. Chakravarty and A. Chakravorty, Inorg. Chem., 1981, 20, 3138; N. Bag, G. K. Lahiri and A. Chakravorty, J. Chem. Soc., Dalton Trans., 1990, 1557; G. K. Lahiri, S. Bhattacharya, M. Mukherjee, A. K. Mukherjee and A. Chakravorty, Inorg. Chem., 1987, 26, 3359; G. K. Lahiri, S. Bhattacharya, B. K. Ghosh and A. Chakravorty, Inorg. Chem., 1987, 26, 4324; H. K. Gupta and S. Dikshit, Polyhedron, 1987, 6, 1009; N. S. Hush and A. Edgar, Chem. Phys. Lett., 1980, 69, 128; K. Matsumoto, T. Matsumoto, M. Kawano, H. Ohnuki, Y. Shichi, T. Nishide and T. Sato, J. Am. Chem. Soc., 1996, 118, 3597.
30. C. Joachim, S. P. Launay and S. Woitellier, Chem. Phys., 1990, 147, 131; J. P. Collin and J. P. Sauvage, J. Am. Chem. Soc., 1998, 120, 3717.
31. A. B. P. Lever, work in progress.
32. A. Freda, undergraduate thesis project.