A novel type of resonance-stabilised dicobalt complex with a cyclopentadienylidene bridge - Synthesis, structure and electronic properties of [(C5R5)Co(μ-C5H4)Co(L)(C 5R5)′] (L = C2H4, CO, CNtBu, PR3, P(OMe)3; R = H, Me)

Chemistry - A European Journal

Volumn 2, Issue 11, 1996, Pages 1453-1465

  Wadepohl, Hubert ^a   Galm, Wolfgang ^a   Pritzkow, Hans ^a   Wolf, Andreas ^a  

^a UNIVERSITY OF HEIDELBERG   (Germany)

Author keywords

Carbenes; CH activation; Dinuclear complexes; Sandwich complexes; Spin equilibria

Indexed keywords

C-H ACTIVATION; CARBENES; DINUCLEAR COMPLEX; SANDWICH COMPLEXES; SPIN EQUILIBRIA;

CHEMICAL ACTIVATION; ELECTRONIC PROPERTIES; ETHYLENE; LIGANDS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; ORGANIC COMPOUNDS; PHOSPHORUS COMPOUNDS;

ELECTRON SPIN RESONANCE SPECTROSCOPY;

EID: 0010258712     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.19960021119     Document Type: Article

References (127)

1. H. Wadepohl, Comments Inorg. Chem., 1994, 15, 369 and references therein.
2. H. Wadepohl, S. Gebert, Coord. Chem. Rev. 1995, 143, 535 and references therein.
3. H. Wadepohl, T. Borchert, K. Büchner, H. Pritzkow, Chem. Ber. 1993, 126, 1615.
4. H. Wadepohl, T. Borchert, H. Pritzkow, J. Chem. Soc. Chem. Commun. 1995, 1447.
5. a) H. Wadepohl, W. Galm, H. Pritzkow, Angew. Chem. 1989, 101, 357;
6. Angew. Chem. Int. Ed. Engl. 1989, 28, 345.
7. b) H. Wadepohl, W. Galm, H. Pritzkow, Organometallics 1996, 15, 570.
8. H. Wadepohl, H. Pritzkow, Angew. Chem. 1987, 99, 132;
9. Angew. Chem. Int. Ed. Engl. 1987, 26, 127.
10. a) T. L. Gilchrist, C. W. Rees, Carbene, Nitrene und Dehydroaromaten, A. Hüthig, Heidelberg 1972, Chapt. 5.
11. b) H. Dürr, Top. Curr. Chem. 1973, 40, 103;
12. ibid. 1975, 55, 87 and references therein.
13. c) H. Dürr, F. Werndorff, Angew. Chem. 1974, 86, 413;
14. Angew. Chem. Int. Ed. Engl. 1974, 13, 483.
15. d) C. Wentrup, Reaktive Zwischenstufen I, Thieme, Stuttgart 1979, Chapt. 4.
16. a) R. Gleiter, R. Hoffmann, J. Am. Chem. Soc. 1968, 90, 5457.
17. b) M. Z. Kassaee, M. R. Nimlos, K. E. Downie, E. E. Waali, Tetrahedron 1985, 41, 1579.
18. c) J. M. Bofill, N. Bru, J. Farràs, S. Olivella, A. Solé, J. Vilarrasa, J. Am. Chem. Soc. 1988, 110, 3740.
19. Systems where an electron donor is electronically coupled to an electron acceptor by a π bridge form the most important class of NLO compounds [N. J. Long, Angew. Chem. 1995, 107, 37;
20. Angew. Chem. Int. Ed. Engl. 1995, 34, 21.
21. T. J. Marks, M. A. Ratner, ibid. 1995, 107, 167
22. and 1995, 34, 155].
23. Recently, high hyperpolarisabilities have been reported for bimetallic sandwich-type complexes: U. Behrens, H. Brussaard, U. Hagenau, J. Heck, E. Hendrickx, J. Körnich, J. G. M. v. d. Linden, A. Persoons, A. L. Spek, N. Veldman, B. Voss, H. Wong, Chem. Eur. J. 1996, 2, 98.
24. a) S. Gambarotta, C. Floriani, A. Chiesi-Villa, C. Guastini, J. Organomet. Chem. 1985, 296, C6.
25. b) H. Wadepohl, H. Pritzkow, Polyhedron 1989, 8, 1939.
26. H. Werner, R. Feser, V. Harder, W. Hofmann, H. Neukomm, Inorg. Synth. 1989, 25, 158.
27. For a comprehensive overview see H. Dürr in Methoden der Organischen Chemie (Houben-Weyl) (Ed.: M. Regitz), Thieme: Stuttgart 1989, Vol. E 19b.
28. W. Kirmse, Angew. Chem. 1959.
29. a) W. A. Herrmann, Angew. Chem. 1978, 90, 855;
30. Angew. Chem. Int. Ed. Engl. 1978, 17, 800.
31. b) W. A. Herrmann, Adv. Organomet. Chem. 1982, 20, 159.
32. c) W. A. Herrmann, Pure Appl. Chem. 1982, 54, 65.
33. d) W. A. Herrmann, J. Organomet. Chem. 1983, 250, 319.
34. H. Fischer in: Transition Metal Carbene Complexes, Verlag Chemie, Weinheim, 1983, pp. 1-68 and references therein.
35. G. A. Somorjai, Chem. Soc. Rev. 1984, 13, 321 and references therein.
36. 5H5́: a) E. L. Muetterties, personal communication, 1983.
37. b) N. Avery, Surf. Sci. 1984, 137, L109.
38. c) N. Avery, ibid. 1984, 146, 363.
39. d) F. P. Netzer, A. Goldmann, G. Rosina, E. Bertel, ibid. 1988, 204, 387.
40. a) E. O. Fischer, G. Herberich, Chem. Ber. 1961 94, 1517.
41. b) M. L. H. Green, L. Pratt, G. Wilkinson, J. Chem. Soc. 1959, 3753.
42. c) P. L. Pauson, J. Organomet. Chem. 1980, 200, 207.
43. d) G. R. Knox, M. Nutley, P. L. Pauson, S. Thoma, P. E. Watts, P. E. Elder, R. Griffiths, J. Chem. Research (M) 1981, 1901.
44. Abstraction of the endo hydrogen has been observed in some exo-substituted derivatives of 4: N. El Murr, J. Organomet. Chem. 1981, 208, C9.
45. I. U. Khand, P. L. Pauson, W. E. Watts, J. Chem. Soc. (C) 1969, 2024.
46. n rings have been observed [18d, 22].
47. a) W. R. Roth, W. Grimme, Tetrahedron Lett. 1966, 21, 2347.
48. b) M. I. Foreman, G. R. Knox, P. L. Pauson, K. H. Todd, W. E. Watts, J. Chem. Soc. Perkin Trans. II 1972, 1141.
49. c) J. W. Faller, Inorg. Chem. 1980, 19, 2857.
50. d) J. M. Brown, I. Midgley, W. J. Albery, J. Chem. Soc. Perkin Trans. II 1982, 767.
51. e) M. L. H. Green, P. A. Newman, J. A. Bandy, J. Chem. Soc. Dalton Trans. 1989, 331.
52. W. A. Herrmann, J. Plank, M. L. Ziegler, K. Weidenhammer, Angew. Chem. 1978, 90, 817;
53. Angew. Chem. Int. Ed. Engl. 1978, 17, 777.
54. 3 cyclopentadienylidene bridges is also known: a) N. D. Feasey, N. J. Forrow, G. Hogarth, S. A. R. Knox, K. A. Macpherson, M. J. Morris, A. G. Orpen, J. Organomet. Chem. 1984, 267, C41.
55. b) A. J. Deeming. N. I. Powell, C. Whittacker, J. Chem. Soc. Dalton Trans. 1991, 1875.
56. a) W. A. Herrmann, C. Bauer, J. Plank, W. Kalcher, D. Speth, M. L. Ziegler, Angew. Chem. 1981, 93, 212;
57. Angew. Chem. Int. Ed. Engl. 1981, 20, 193.
58. b) N. M. Boag, M. Green, M. R. Mills, G. N. Pain, F. G. A. Stone, J. Chem. Soc. Chem. Commun. 1980, 1171.
59. c) A. D. Clauss, P. A. Dimas. J. R. Shapley, J. Organomet. Chem. 1980, 201, C31
60. d) W. A. Herrmann, C. Bauer, G. Kriechbaum, H. Kunkeley, D. Speth, E. Guggolz, Chem. Ber. 1982, 115, 878.
61. e) W. A. Herrmann, J. Plank, C. Bauer, M. L. Ziegler, E. Guggolz, R. Alt, Z. Anorg. Allg. Chem. 1982, 487, 85.
62. f) W. A. Herrmann, C. Bauer, Chem. Ber. 1982, 115, 14.
63. g) W. A. Herrmann, G. Kriechbaum, C. Bauer, E. Guggolz, M. L. Ziegler, Angew. Chem. 1981, 93, 838;
64. Angew. Chem. Int. Ed. Engl. 1981, 20, 815.
65. A. A. Danopoulos, G. Wilkinson, D. J. Williams, J. Chem. Soc. Chem. Commun. 1991, 181.
66. Usually, the double-headed arrow stands between "resonance structures". The strict definition of resonance implies that the true electronic structure of a compound may be considered as a mixture of several nonexistant resonance structures with the same geometry, but a different arrangement of localised bonds (see for example J. March, Advanced Organic Chemistry, McGraw-Hill, New York, 2nd ed. 1977, Chapt. 2). Lacking a pre-defined symbol, in the context of this paper we use the double-headed arrow to indicate a continuum between two limiting structures (which may indeed exist) with different geometry and bonding.
67. a) G. P. Pez, J. Am. Chem. Soc. 1976, 98, 8072.
68. b) C. Couldwell, K. Prout, Acta Crystallogr. Sect. B, 1979, 35, 335.
69. c) R. J. Hoxmeier, C. B. Knobler, H. D. Kaesz, Inorg. Chem. 1979, 18, 3462.
70. d) B. Meunier, K. Prout, Acta Crystallogr. Sect. B, 1979, 35, 2558.
71. e) C. Couldwell, K. Prout, ibid. 1979, 35, 335.
72. f) D. A. Lemenovskii, V. P. Fedin, A. V. Aleksandrov, Y. L. Solokotov, Y. T. Struchkov, J. Organomet. Chem. 1981, 201, 257.
73. g) A. A. Pasynskii, Y. V. Skripkin, V. T. Kalinnikov, M. A. Porai-Koshits, A. S. Antsyshkina, G. G. Sadikov, V. N. Ostrikova, ibid. 1981, 201, 269.
74. More recently, further examples have been reported: h) M. L. H. Green, M. L. Poveda, J. Bashkin, K. Prout, J. Chem. Soc. Chem. Commun. 1982, 30.
75. i) J. Bashkin, M. L. H. Green, M. L. Poveda, K. Prout, J. Chem. Soc. Dalton Trans. 1982, 2485.
76. j) J. Bashkin, M. L. H. Green, M. L. Poveda, K. Prout, ibid. 1982, 2485.
77. k) G. P. Pez, P. Apgar, R. K. Crissey, J. Am. Chem. Soc. 1982, 104, 482.
78. l) K. P. C. Vollhardt, T. W. Weidman, ibid. 1983, 105, 1676.
79. m) F. H. Köhler, W. A. Geike, P. Hofmann, U. Schubert, P. Stauffert, Chem. Ber. 1984, 117, 904.
80. n) C. P. Casey, R. E. Palermo, R. F. Jordan, A. L. Rheingold, J. Am. Chem. Soc. 1985, 107, 4597.
81. o) T. T. Wenzel, R. G. Bergman, ibid. 1986, 108, 4856.
82. p) L. B. Kool, M. D. Rausch, H. G. Alt, M. Herberhold, U. Thewalt, B. Honold, J. Organomet. Chem. 1986, 310, 27.
83. q) M. W. Droege, W. D. Harman, H. Taube, Inorg. Chem. 1987, 26, 1309.
84. r) D. H. Berry, T. S. Koloski, P. J. Carroll, Organometallics, 1990, 9, 2952.
85. s) J. Ho, D. W. Stephan, ibid. 1992, 11, 1014.
86. a) D. W. Macomber, R. D. Rogers, ibid. 1985, 4, 1485.
87. b) G. Erker, R. Lecht, C. Krüger, Y.-H. Tsay, H. Bönnemann, J. Organomet. Chem. 1987, 326, C 75.
88. c) G. Erker, R. Lecht, J. L. Petersen, H. Bönnemann, Organometallics 1987, 6, 1962.
89. d) A. C. Filippou, E. Herdtweck, H. G. Alt, J. Organomet. Chem. 1988, 355, 437.
90. e) L. Qiwing, H. Xiang, L. Shutang, Y. Hong, W. Binfang, J. Zhenxing, S. Jianqiu, Polyhedron 1993, 12, 1527.
91. f) F. Carre, G. Cerveau, E. Colomer, R. J. P. Corriu, J. C. Young, L. Richard, R. Weiss, J. Organomet. Chem. 1979, 179, 215.
92. g) A. W. Coleman, P. B. Hitchcock, M. F. Lappert, R. K. Maskell, J. H. Müller, ibid. 1983, 250, C9.
93. P. Hofmann, M. Padmanabhan, Organometallics 1983, 2, 1273.
94. H. Wadepohl, W. Galm, H. Pritzkow, A. Wolf, J. Chem. Soc. Chem. Commun. 1993, 1459.
95. An overview of the literature may be found in H. Wadepohl, Dissertation, Universität Marburg 1982.
96. Important review articles: a) D. R. Eaton, W. D. Phillips, Adv. Magn. Resonance 1965, 103, 1.
97. b) E. de Boer, H. van Willigen, Progr. NMR Spectrosc. 1967, 2, 111.
98. c) H. J. Keller in P. Diehl, E. Fluck, R. Koesfeld (eds.) NMR, Basic Principles and Progress 2, Springer Verlag, Berlin 1970.
99. d) G. N. LaMar, W. De W. Horrocks, Jr., R. D. Holm (eds.) NMR of Paramagnetic Molecules: Priciples and Applications, Academic Press, London 1973.
100. P. S. Pregosin, R. W. Kunz in NMR, Basic Principles and Progress 16 (Eds.: P. Diehl, E. Fluck, R. Koesfeld), Springer Verlag, Berlin 1979.
101. R. R. Ernst, G. Bodenhausen, A. Wokaun, Principles of Nuclear Magnetic Resonance in One and Two Dimensions, Clarendon Press, Oxford 1987, Ch.2.3.
102. a) W. L. Olson, A. M. Stacy, L. F. Dahl, J. Am. Chem. Soc. 1986, 108, 7646.
103. b) B. Bachmann, F. Hahn, J. Heck, M. Wünsch, Organometallics 1989, 8, 2523.
104. Only the resonances of the CH and Cp protons were included in the fitting procedure.
105. D. C. Calabro, J. L. Hubbard, C. H. Blevins II, A. C. Campbell, D. L. Lichtenberger, J. Am. Chem. Soc. 1981, 103, 6839.
106. a) E. O. Fischer, W. Pfab, Z. Naturforsch. Sect. B 1952, 7, 377.
107. b) G. Wilkinson, J. Am. Chem. Soc. 1952, 74, 6148.
108. c) E. O. Fischer, R. Jira, Z. Naturforsch. Sect. B 1953, 8, 327.
109. H. Wadepohl, W. Galm, H. Pritzkow, A. Wolf, Angew. Chem. 1992, 104, 1050:
110. Angew. Chem. Int. Ed. Engl. 1992, 104, 1058.
111. K. Jonas, J. Organomet. Chem. 1990, 400, 165.
112. a) R. Gleiter, R. Seeger, Helv. Chim. Acta 1971, 54, 123.
113. b) R. Gleiter, R. Seeger, H. Binder, E. Fluck, M. Cais, Angew. Chem. 1972, 84, 1107;
114. Angew. Chem. Int. Ed. Engl. 1972, 11, 1028.
115. c) J. J. Dannenberg, M. K. Levenberg, J. H. Richards, Tetrahedron 1973, 29, 1575
116. d) U. Behrens, J. Organomet. Chem. 1979, 182, 89.
117. a) H. Wadepohl, Habilitationsschrift, Universität Heidelberg, 1989
118. b) D. Rau, U. Behrens, J. Organomet. Chem. 1990, 387, 219.
119. c) H. Wadepohl, H. Pritzkow, Acta Crystallogr. Sect. C: Struct. Commun. 1991, C 47, 2061.
120. a) K. Jonas, E. Deffense, D. Habermann, Angew. Chem. 1983, 95, 729;
121. Angew. Chem. Int. Ed. Engl. 1983, 22, 716.
122. b) K. Jonas, E. Deffense, D. Habermann, Angew. Chem. Suppl. 1983, 1005.
123. S. A. Frith, J. L. Spencer, Inorg. Synth. 1985, 23, 15.
124. a) SHELXS-86, G. M. Sheldrick, Acta Crystallogr. 1990, A 46, 467.
125. SHELXL-93, G. M. Sheldrick, Universität Göttingen 1993.
126. ORTEP-II, C. K. Johnson, Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.
127. F. Hahn, AUTOZYK. Universität Marburg 1987.