Synthesis, characterisation and reactivity of hydrazine complexes of iron(II)

Abstract

Hydrazine complexes [Fe(R¹NHNH₂)(R²CN)L₄][BPh₄]₂ 1–3 and [FeH(R¹NHNH₂)L₄]BPh₄ 4 [R¹ = H, Me, Ph, 4-MeC₆H₄, 4-ClC₆H₄, 4-O₂NC₆H₄ or Me₂NNH₂; R² = 4-MeC₆H₄, Me or Ph; L = P(OEt)₃, P(OMe)₃ or PPh(OEt)₂] were prepared by reacting nitrile complexes [Fe(R²CN)₂L₄][BPh₄]₂ and [FeH(R²CN)L₄]BPh₄ with an excess of the appropriate hydrazine. Their formulation and geometry in solution were established by infrared and ¹H and ³¹P NMR spectroscopy. Amidrazone derivatives [Fe{η²-NH[double bond, length half m-dash]C(R²)NR¹NH₂}L₄][BPh₄]₂ [R² = 4-MeC₆H₄, Me or Ph; R¹ = H or Me; L = P(OEt)₃ or P(OMe)₃] were obtained by allowing nitrilehydrazine complexes to react in solution and their formation, involving a nucleophilic attack of the hydrazine on the cyanide carbon atom of the R²CN ligand, is also discussed. Reaction of the arylhydrazine complexes 1–4 with Pb(O₂CMe)₄ at –30 °C in CH₂Cl₂ resulted in selective oxidation of the arylhydrazine ligand affording the aryldiazene [Fe(R¹N[double bond, length half m-dash]NH)(R²CN)L₄][BPh₄]₂ and [FeH(R¹N[double bond, length half m-dash]NH)L₄]BPh₄ 10 [R¹ = aryl; L = P(OEt)₃ or P(OMe)₃] derivatives. Treatment of the arylhydrazine [Fe(R¹NHNH₂)(R²CN){P(OEt)₃}₄][BPh₄]₂ 1 (R¹ = Ph or 4-MeC₆H₄) with an excess of NEt₃ resulted in a complicated reaction giving the five-co-ordinate aryldiazenido derivatives [Fe(R¹N₂){P(OEt)₃}₄]BPh₄.

References

1. D. Sutton, Chem. Rev., 1993, 93, 995; H. Kisch and P. Holzmeier, Adv. Organomet. Chem., 1992, 34, 67; B. F. G. Johnson, B. L. Haymore and J. R. Dilworth, in Comprehensive Coordination Chemistry, eds. G. Wilkinson, R. D. Gillard and J. A. McCleverty, Pergamon, Oxford, 1987, vol. 2, p. 130; R. A. Henderson, G. J. Leigh and C. J. Pickett, Adv. Inorg. Chem. Radiochem., 1983, 27, 197; W. A. Nugent and B. L. Haymore, Coord. Chem. Rev., 1980, 31, 123; F. Bottomley, Q. Rev. Chem. Soc., 1970, 24, 617.
2. M. Hidai and Y. Mizobe, Chem. Rev., 1995, 95, 1115; R. R. Eady and G. J. Leigh, J. Chem. Soc., Dalton Trans., 1994, 2739; D. Sellmann, Angew. Chem., Int. Ed. Engl., 1993, 32, 64.
3. (a) K. D. Demadis, S. M. Malinak and D. Coucouvanis, Inorg. Chem., 1996, 35, 4038; (b) C. J. Davies, I. M. Dodd, M. M. Harding, B. T. Heaton, C. Jacob and J. Ratnam, J. Chem. Soc., Dalton Trans., 1994, 787; (c) T.-Y. Cheng, A. Ponce, A. L. Rheingold and G. L. Hillhouse, Angew. Chem., Int. Ed. Engl., 1994, 33, 657; (d) D. Sellmann, J. Käppler, M. Moll and F. Knoch, Inorg. Chem., 1993, 32, 960; (e) T. E. Glassman, M. G. Vale and R. R. Schrock, J. Am. Chem. Soc., 1992, 114, 8098; (f) M. Kawano, C. Hoshino and K. Matsumoto, Inorg. Chem., 1992, 31, 5158.
4. B. K. Burgess, S. Wherland, E. I. Stiefel and W. E. Newton, Biochemistry, 1981, 20, 5140; L. C. Davies, Arch. Biochem. Biophys., 1980, 204.
5. M. J. Dilworth and R. R. Eady, Biochem. J., 1991, 277, 465; R. N. Thorneley and D. J. Lowe, Biochem. J., 1984, 224, 887; D. J. Evans, R. A. Henderson and B. E. Smith, in Bioinorganic Catalysis, ed. J. Reedijk, Marcel Dekker, New York, 1993; R. N. Thorneley, R. R. Eady and D. J. Lowe, Nature, London, 1978, 272, 557.
6. (a) G. Albertin, S. Antoniutti and E. Bordignon, J. Chem. Soc., Chem. Commun., 1984, 1688; (b) G. Albertin, S. Antoniutti, G. Pelizzi, F. Vitali and E. Bordignon, J. Am. Chem. Soc., 1986, 108, 6627; (c) G. Albertin and E. Bordignon, J. Chem. Soc., Dalton Trans., 1986, 2551; (d) G. Albertin, S. Antoniutti and E. Bordignon, Inorg. Chem., 1987, 26, 3416; (e) G. Albertin, S. Antoniutti, G. Pelizzi, F. Vitali and E. Bordignon, Inorg. Chem., 1988, 27, 829; (f) G. Albertin, S. Antoniutti and E. Bordignon, J. Am. Chem. Soc., 1989, 111, 2072; (g) G. Albertin, S. Antoniutti and E. Bordignon, J. Chem. Soc., Dalton Trans., 1989, 2553; (h) G. Albertin, P. Amendola, S. Antoniutti and E. Bordignon, J. Chem. Soc., Dalton Trans., 1990, 2979; (i) G. Albertin, S. Antoniutti, A. Bacchi, E. Bordignon, G. Pelizzi and P. Ugo, Inorg. Chem., 1996, 35, 6245.
7. G. Albertin, S. Antoniutti, A. Bacchi, E. Bordignon, P. M. Dolcetti and G. Pelizzi, preceding paper.
8. D. Sellmann, T. Becker, T. Hofmann, F. Knoch and M. Moll, Inorg. Chim. Acta, 1994, 219, 75; D. Sellmann, W. Soglowek, F. Knoch, G. Ritter and J. Dengler, Inorg. Chem., 1992, 31, 3711; D. Sellmann, H. Kunstmann, F. Knoch and M. Moll, Inorg. Chem., 1988, 27, 4183; D. Sellmann and U. Reineke, J. Organomet. Chem., 1986, 314, 91; D. Sellmann and U. Kleine-Kleffmann, J. Organomet. Chem., 1983, 247, 307.
9. A. Ferrari, A. Braibanti and A. M. Lanfredi, Ann. Chim., 1958, 48, 1238; D. Nicholls and R. Swindells, J. Inorg. Nucl. Chem., 1968, 30, 2211; V. A. Starodub, M. S. Novakovskii, V. G. Kirichenko, V. V. Chekin and A. I. Velikodnyi, Koord. Chim., 1975, 1, 1706; A. Anagnostopoulos, D. Nicholls and J. Reed, Inorg. Chim. Acta, 1979, 32, L17; P. Glavic, J. Slivnik and A. Bole, J. Inorg. Nucl. Chem., 1980, 42, 1781.
10. (a) E. O. Fischer and E. Moser, J. Organomet. Chem., 1966, 5, 63; (b) D. Sellmann and E. Kleinschmidt, J. Organomet. Chem., 1977, 140, 211; (c) S. Antoniutti, G. Albertin and E. Bordignon, Inorg. Chem., 1987, 26, 2733.
11. R. Rabinowitz and J. Pellon, J. Org. Chem., 1961, 26, 4623.
12. E. Nachbaur and G. Leiseder, Monatsh. Chem., 1971, 102, 1718.
13. G. Balacco, J. Chem. Inf. Comput. Sci., 1994, 34, 1235.
14. W. J. Geary, Coord. Chem. Rev., 1971, 7, 81.
15. K. M. Watson and D. G. Neilson, in The Chemistry of Amidines and Imidates, ed. S. Patai, Wiley, London, 1975, p. 491.
16. L. Maresca, G. Natile, F. P. Intini, F. Gasparrini, A. Tiripicchio and M. Tiripicchio Camellini, J. Am. Chem. Soc., 1986, 108, 1180; F. P. Fanizzi, F. P. Intini and G. Natile, J. Chem. Soc., Dalton Trans., 1989, 947; R. Cini, F. P. Fanizzi, F. P. Intini, L. Maresca and G. Natile, J. Am. Chem. Soc., 1993, 115, 5123; P. Paul and K. Nag, Inorg. Chem., 1987, 26, 1586; D. L. Thorn and J. C. Calabrese, J. Organomet. Chem., 1984, 272, 283.
17. (a) C. A. Amodio and K. B. Nolan, Inorg. Chim. Acta, 1986, 113, 27; (b) A. Syamala and A. R. Chakravarty, Inorg. Chem., 1991, 30, 4699; (c) S. G. Feng, P. S. White and J. L. Templeton, Organometallics, 1993, 12, 1765; (d) D. P. Fairlie and W. G. Jackson, Inorg. Chem., 1990, 29, 140.
18. (a) T. Uchiyama, K. Takagi, K. Matsumoto, S. Ooi, Y. Nakamura and S. Kawaguchi, Chem. Lett., 1979, 1197; Bull. Chem. Soc. Jpn., 1981, 54, 1077; (b) Z. Kanda, Y. Nakamura and S. Kawaguchi, Inorg. Chem., 1978, 17, 910; (c) R. A. Michelin, M. Mozzon, P. Berin, R. Bertani, F. Benetollo, G. Bombieri and R. J. Angelici, Organometallics, 1994, 13, 1341; (d) P. Braunstein, D. Matt, Y. Dusausoy and J. Fischer, Organometallics, 1983, 2, 1410; (e) J. Vicente, M.-T. Chicote, J. Fernandez-Baeza, F. J. Lahoz and J. A. Lopez, Inorg. Chem., 1991, 30, 3617.
19. R. A. Michelin, M. Mozzon and R. Bertani, Coord. Chem. Rev., 1996, 147, 299.
20. C. A. Tolman, Chem. Rev., 1977, 77, 313; M. M. Rahman, H.-Y. Liu, K. Eriks, A. Prock and W. P. Giering, Organometallics, 1989, 8, 1.
21. (a) M. R. Smith, III, T.-Y. Cheng and G. L. Hillhouse, J. Am. Chem. Soc., 1993, 115, 8638; (b) D. Sellmann, J. Käppler, M. Moll and F. Knoch, Inorg. Chem., 1993, 32, 960; (c) D. Sellmann, W. Soglowek, F. Knoch and M. Moll, Angew. Chem., Int. Ed. Engl., 1989, 28, 1271; (d) M. R. Smith, III, R. L. Keys, G. L. Hillhouse and A. L. Rheingold, J. Am. Chem. Soc., 1989, 111, 8312; (e) D. Sellmann and K. Jödden, Angew. Chem., Int. Ed. Engl., 1977, 16, 464.