Novel synthetic routes to the anionic alkylidene complex [Cp*Mo(NO)(CH2SiMe3)(=CHSiMe3)] - from its neutral dialkyl precursor

Organometallics

Volumn 15, Issue 19, 1996, Pages 3907-3909

  Legzdins, Peter ^a   Sayers, Stephen F ^a  

^a UNIVERSITY OF BRITISH COLUMBIA   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000719890     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om960399t     Document Type: Article

References (48)

1. Schrack, R. R. J. Am. Chem. Soc. 1974, 96, 6796.
2. Feldman, J.; Schrock, R. R. Prog, Inorg. Chem. 1991, 39, 1 and references therein.
3. Several transition-metal alkylidene complexes are efficient olefin metathesis catalysts; see: Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100 and references cited therein.
4. 3)-Li has been reported, but definitive NMR spectroscopic evidence for its formulation has not been obtained; see: Schumann, H.; Muller, J. J. Organomet. Chem. 1979, 169, C1.
5. 2(=CHPh)]-anion has been postulated as a reaction intermediate, but it has not been isolated; see: Winter, M. J.; Woodward, S. J. Organomet. Chem. 1989, 361, C18.
6. 3, has been fully characterized; see: Schrock, R. R.; Luo, S.; Lee, J. C.; Zanetti, N. C.; Davis, W. M. J. Am. Chem. Soc. 1996, 118, 3883.
7. Deprotonation of an alkyl ligand in an organometallic cation is a known route to neutral alkylidene complexes; see. for instance: (a) Schrock, R. R. J. Am. Chem. Soc. 1975, 97, 6577. (b) Schrock, R. R.; Sharp, P. R. J. Am. Chem. Soc. 1978, 100, 2389.
8. Deprotonation of an alkyl ligand in an organometallic cation is a known route to neutral alkylidene complexes; see. for instance: (a) Schrock, R. R. J. Am. Chem. Soc. 1975, 97, 6577. (b) Schrock, R. R.; Sharp, P. R. J. Am. Chem. Soc. 1978, 100, 2389.
9. Legzdins, P.; Landmark, P. J.; Phillips, E. C.; Rettig, S. J.; Veltheer, J. E. Organometallics 1992, 11, 2991.
10. 6): δ -3.0 (s).
11. (a) Legzdins, P.; Richter-Addo, G. B. Metal Nitrosyls; Oxford University Press: New York, 1992; p 276.
12. (b) Lee, K. E.; Arif, A. M.; Gladysz, J. A. Inorg. Chem. 1990, 29, 2885.
13. o) and 571 variables. Full details of this structure determination will be published elsewhere.
14. See caption to Figure 1.
15. 2Ph) exhibits bond lengths of Mo-N = 1.760 (2) Å and N-O = 1.217 (2) Å; see: Dryden, N. H.: Legzdins, P.; Phillips, E. C.; Trotter, J.; Yee, V. C. Organometallics 1990, 9, 882.
16. Torsion angle N (1)-Mo(1)-C(2)-Si(2) = 5.1°.
17. (a) Gibson, V. C. J. Chem. Soc., Dalton Trans. 1994, 1607.
18. (b) Herrmann, W. A.; Hubbard, J. L.; Bernal, I.; Korp. J. D.; Haymore, B. L.; Hillhouse, G. L. Inorg. Chem. 1984, 23, 2978.
19. (c) Schilling, B. E. R.; Hoffmann, R.; Faller, J. W. J. Am. Chem. Soc. 1979, 101, 592.
20. (a) Legzdins, P.; Rettig, S. J.; Veitheer, J. E. J. Am. Chem. Soc. 1992, 114, 6922.
21. (b) Legzdins, P.; Rettig, S. J.; Veltheer, J. E.; Batchelor, R. J.; Einstein, P. W. B. Organometallics 1993, 12, 3575.
22. 6): δ-3.5 (s).
23. 2)-containing complexes are known; see: (a) Huber, S. R.; Baldwin, T. C.; Wigley, D. E. Organometallics 1993, 12, 91. (b) Schock, L. E.; Brock, C. P.; Marks, T. J. Organometallics 1987, 6, 232.
24. 2)-containing complexes are known; see: (a) Huber, S. R.; Baldwin, T. C.; Wigley, D. E. Organometallics 1993, 12, 91. (b) Schock, L. E.; Brock, C. P.; Marks, T. J. Organometallics 1987, 6, 232.
25. Debad, J. D.; Legzdins, P.; Rettig, S. J.; Veltheer, J. E. Organometallics 1993, 12, 2714.
26. 2Hf=CHPh) to its "tucked-in" isomer; see: Bulls, A. R.; Schaefer, W. P.; Serfas, M.; Bercaw, J. E. Organometallics 1987, 6, 1219.
27. 2 coproduct has also been isolated from the final reaction mixture and characterized by its mass spectral and NMR spectroscopic data.
28. Similar conversions of cationic 17e alkyl complexes to cationic 18e alkylidene complexes by hydrogen-atom abstraction have been documented; see: (a) Hayes, J. C.; Jernakoff, P.; Miller, G. A.; Cooper, N. J. Pure Appl. Chem. 1984, 56, 25. (b) Jernakoff, P.; Cooper, N. J. Organometallics 1986, 5, 747.
29. Similar conversions of cationic 17e alkyl complexes to cationic 18e alkylidene complexes by hydrogen-atom abstraction have been documented; see: (a) Hayes, J. C.; Jernakoff, P.; Miller, G. A.; Cooper, N. J. Pure Appl. Chem. 1984, 56, 25. (b) Jernakoff, P.; Cooper, N. J. Organometallics 1986, 5, 747.
30. Herring, F. G.; Legzdins, P.; Richter-Addo, G. B. Organometallics 1989, 8, 1485.
31. Due to its extreme air sensitivity, a satisfactory elemental analysis of 4 could not be obtained.
32. w = 0.031 for 1939 reflections with I ≥ 3σ(I). Full details of this structure determination will be published elsewhere.
33. For examples of similar three-coordinate lithium centers see: (a) Hvoslef, J.; Hope, H.; Murray, B. D.; Power, P. P. J. Chem. Soc., Chem. Commun. 1983, 1438. (b) Huffman, J. C.; Geerts, R. L.; Caulton, K. G. J. Cryst. Spectrosc. 1984, 14, 541. (c) Becker. G.; Hartmann, H.-M.; Munch, A.; Riffel, H. Z. Anorg. Allg. Chem. 1985, 29, 530. (d) Engelhardt, L. M.; Harrowfield, J. M.; Lappert, M. F.; MacKinnon, I. A.; Newton, B. H.; Raston, C. L.; Skelton, B. W.; White, A. H. J. Chem. Soc., Chem. Commun. 1986, 846. (e) Weese, K. H.; Bartlett, R. A.; Murray, B. D.; Olmstead, M. M.; Power, P. P. Inorg. Chem. 1987, 26, 2409. (f) Askham, F. R.; Carroll, K. M.; Alexander, S. J.; Rheingold, A. L.; Haggerty, B. S. Organometallics 1993, 12, 4810. [Obtained from the Cambridge Structural Data Base: Allen, F. H.; Kennard, O. Chem. Disign Automation News 1993, 8, 31.]
34. For examples of similar three-coordinate lithium centers see: (a) Hvoslef, J.; Hope, H.; Murray, B. D.; Power, P. P. J. Chem. Soc., Chem. Commun. 1983, 1438. (b) Huffman, J. C.; Geerts, R. L.; Caulton, K. G. J. Cryst. Spectrosc. 1984, 14, 541. (c) Becker. G.; Hartmann, H.-M.; Munch, A.; Riffel, H. Z. Anorg. Allg. Chem. 1985, 29, 530. (d) Engelhardt, L. M.; Harrowfield, J. M.; Lappert, M. F.; MacKinnon, I. A.; Newton, B. H.; Raston, C. L.; Skelton, B. W.; White, A. H. J. Chem. Soc., Chem. Commun. 1986, 846. (e) Weese, K. H.; Bartlett, R. A.; Murray, B. D.; Olmstead, M. M.; Power, P. P. Inorg. Chem. 1987, 26, 2409. (f) Askham, F. R.; Carroll, K. M.; Alexander, S. J.; Rheingold, A. L.; Haggerty, B. S. Organometallics 1993, 12, 4810. [Obtained from the Cambridge Structural Data Base: Allen, F. H.; Kennard, O. Chem. Disign Automation News 1993, 8, 31.]
35. For examples of similar three-coordinate lithium centers see: (a) Hvoslef, J.; Hope, H.; Murray, B. D.; Power, P. P. J. Chem. Soc., Chem. Commun. 1983, 1438. (b) Huffman, J. C.; Geerts, R. L.; Caulton, K. G. J. Cryst. Spectrosc. 1984, 14, 541. (c) Becker. G.; Hartmann, H.-M.; Munch, A.; Riffel, H. Z. Anorg. Allg. Chem. 1985, 29, 530. (d) Engelhardt, L. M.; Harrowfield, J. M.; Lappert, M. F.; MacKinnon, I. A.; Newton, B. H.; Raston, C. L.; Skelton, B. W.; White, A. H. J. Chem. Soc., Chem. Commun. 1986, 846. (e) Weese, K. H.; Bartlett, R. A.; Murray, B. D.; Olmstead, M. M.; Power, P. P. Inorg. Chem. 1987, 26, 2409. (f) Askham, F. R.; Carroll, K. M.; Alexander, S. J.; Rheingold, A. L.; Haggerty, B. S. Organometallics 1993, 12, 4810. [Obtained from the Cambridge Structural Data Base: Allen, F. H.; Kennard, O. Chem. Disign Automation News 1993, 8, 31.]
36. For examples of similar three-coordinate lithium centers see: (a) Hvoslef, J.; Hope, H.; Murray, B. D.; Power, P. P. J. Chem. Soc., Chem. Commun. 1983, 1438. (b) Huffman, J. C.; Geerts, R. L.; Caulton, K. G. J. Cryst. Spectrosc. 1984, 14, 541. (c) Becker. G.; Hartmann, H.-M.; Munch, A.; Riffel, H. Z. Anorg. Allg. Chem. 1985, 29, 530. (d) Engelhardt, L. M.; Harrowfield, J. M.; Lappert, M. F.; MacKinnon, I. A.; Newton, B. H.; Raston, C. L.; Skelton, B. W.; White, A. H. J. Chem. Soc., Chem. Commun. 1986, 846. (e) Weese, K. H.; Bartlett, R. A.; Murray, B. D.; Olmstead, M. M.; Power, P. P. Inorg. Chem. 1987, 26, 2409. (f) Askham, F. R.; Carroll, K. M.; Alexander, S. J.; Rheingold, A. L.; Haggerty, B. S. Organometallics 1993, 12, 4810. [Obtained from the Cambridge Structural Data Base: Allen, F. H.; Kennard, O. Chem. Disign Automation News 1993, 8, 31.]
37. For examples of similar three-coordinate lithium centers see: (a) Hvoslef, J.; Hope, H.; Murray, B. D.; Power, P. P. J. Chem. Soc., Chem. Commun. 1983, 1438. (b) Huffman, J. C.; Geerts, R. L.; Caulton, K. G. J. Cryst. Spectrosc. 1984, 14, 541. (c) Becker. G.; Hartmann, H.-M.; Munch, A.; Riffel, H. Z. Anorg. Allg. Chem. 1985, 29, 530. (d) Engelhardt, L. M.; Harrowfield, J. M.; Lappert, M. F.; MacKinnon, I. A.; Newton, B. H.; Raston, C. L.; Skelton, B. W.; White, A. H. J. Chem. Soc., Chem. Commun. 1986, 846. (e) Weese, K. H.; Bartlett, R. A.; Murray, B. D.; Olmstead, M. M.; Power, P. P. Inorg. Chem. 1987, 26, 2409. (f) Askham, F. R.; Carroll, K. M.; Alexander, S. J.; Rheingold, A. L.; Haggerty, B. S. Organometallics 1993, 12, 4810. [Obtained from the Cambridge Structural Data Base: Allen, F. H.; Kennard, O. Chem. Disign Automation News 1993, 8, 31.]
38. For examples of similar three-coordinate lithium centers see: (a) Hvoslef, J.; Hope, H.; Murray, B. D.; Power, P. P. J. Chem. Soc., Chem. Commun. 1983, 1438. (b) Huffman, J. C.; Geerts, R. L.; Caulton, K. G. J. Cryst. Spectrosc. 1984, 14, 541. (c) Becker. G.; Hartmann, H.-M.; Munch, A.; Riffel, H. Z. Anorg. Allg. Chem. 1985, 29, 530. (d) Engelhardt, L. M.; Harrowfield, J. M.; Lappert, M. F.; MacKinnon, I. A.; Newton, B. H.; Raston, C. L.; Skelton, B. W.; White, A. H. J. Chem. Soc., Chem. Commun. 1986, 846. (e) Weese, K. H.; Bartlett, R. A.; Murray, B. D.; Olmstead, M. M.; Power, P. P. Inorg. Chem. 1987, 26, 2409. (f) Askham, F. R.; Carroll, K. M.; Alexander, S. J.; Rheingold, A. L.; Haggerty, B. S. Organometallics 1993, 12, 4810. [Obtained from the Cambridge Structural Data Base: Allen, F. H.; Kennard, O. Chem. Disign Automation News 1993, 8, 31.]
39. For examples of similar three-coordinate lithium centers see: (a) Hvoslef, J.; Hope, H.; Murray, B. D.; Power, P. P. J. Chem. Soc., Chem. Commun. 1983, 1438. (b) Huffman, J. C.; Geerts, R. L.; Caulton, K. G. J. Cryst. Spectrosc. 1984, 14, 541. (c) Becker. G.; Hartmann, H.-M.; Munch, A.; Riffel, H. Z. Anorg. Allg. Chem. 1985, 29, 530. (d) Engelhardt, L. M.; Harrowfield, J. M.; Lappert, M. F.; MacKinnon, I. A.; Newton, B. H.; Raston, C. L.; Skelton, B. W.; White, A. H. J. Chem. Soc., Chem. Commun. 1986, 846. (e) Weese, K. H.; Bartlett, R. A.; Murray, B. D.; Olmstead, M. M.; Power, P. P. Inorg. Chem. 1987, 26, 2409. (f) Askham, F. R.; Carroll, K. M.; Alexander, S. J.; Rheingold, A. L.; Haggerty, B. S. Organometallics 1993, 12, 4810. [Obtained from the Cambridge Structural Data Base: Allen, F. H.; Kennard, O. Chem. Disign Automation News 1993, 8, 31.]
40. iso = 1.998 00.
41. For leading references on a variety of transition-metal nitrosyl anions see: (a) Weiner, W. P.; Hollander, F. J.; Bergman, R. G. J. Am. Chem. Soc. 1984, 106, 7462. (b) Crocco, G. L.; Gladysz, J. A. J. Am. Chem. Soc. 1988, 110. 6110. (c) Weng, W.; Bartic, T.; Brady, M.; Bartik, B; Ramsden, J. A.; Arif, A. M.; Gladysz, J. A. J. Am. Chem. Soc. 1995, 117, 11922. (d) McCleverty, J. A.; Seddon, D. J. Chem. Soc., Dalton Trans. 1972, 2526. (e) Cerveau, G.; Colomer, E.; Corriu, R. J. P.; Vioux, A. J. Organomet. Chem. 1987, 321 (3), 327. (f) Jesus, E.; Miguel, A. V.; Royo, P; Lanfredi, A. M. M.; Tiripicchio, A. J. Chem. Soc., Dalton Trans. 1990, 2779.
42. For leading references on a variety of transition-metal nitrosyl anions see: (a) Weiner, W. P.; Hollander, F. J.; Bergman, R. G. J. Am. Chem. Soc. 1984, 106, 7462. (b) Crocco, G. L.; Gladysz, J. A. J. Am. Chem. Soc. 1988, 110. 6110. (c) Weng, W.; Bartic, T.; Brady, M.; Bartik, B; Ramsden, J. A.; Arif, A. M.; Gladysz, J. A. J. Am. Chem. Soc. 1995, 117, 11922. (d) McCleverty, J. A.; Seddon, D. J. Chem. Soc., Dalton Trans. 1972, 2526. (e) Cerveau, G.; Colomer, E.; Corriu, R. J. P.; Vioux, A. J. Organomet. Chem. 1987, 321 (3), 327. (f) Jesus, E.; Miguel, A. V.; Royo, P; Lanfredi, A. M. M.; Tiripicchio, A. J. Chem. Soc., Dalton Trans. 1990, 2779.
43. For leading references on a variety of transition-metal nitrosyl anions see: (a) Weiner, W. P.; Hollander, F. J.; Bergman, R. G. J. Am. Chem. Soc. 1984, 106, 7462. (b) Crocco, G. L.; Gladysz, J. A. J. Am. Chem. Soc. 1988, 110. 6110. (c) Weng, W.; Bartic, T.; Brady, M.; Bartik, B; Ramsden, J. A.; Arif, A. M.; Gladysz, J. A. J. Am. Chem. Soc. 1995, 117, 11922. (d) McCleverty, J. A.; Seddon, D. J. Chem. Soc., Dalton Trans. 1972, 2526. (e) Cerveau, G.; Colomer, E.; Corriu, R. J. P.; Vioux, A. J. Organomet. Chem. 1987, 321 (3), 327. (f) Jesus, E.; Miguel, A. V.; Royo, P; Lanfredi, A. M. M.; Tiripicchio, A. J. Chem. Soc., Dalton Trans. 1990, 2779.
44. For leading references on a variety of transition-metal nitrosyl anions see: (a) Weiner, W. P.; Hollander, F. J.; Bergman, R. G. J. Am. Chem. Soc. 1984, 106, 7462. (b) Crocco, G. L.; Gladysz, J. A. J. Am. Chem. Soc. 1988, 110. 6110. (c) Weng, W.; Bartic, T.; Brady, M.; Bartik, B; Ramsden, J. A.; Arif, A. M.; Gladysz, J. A. J. Am. Chem. Soc. 1995, 117, 11922. (d) McCleverty, J. A.; Seddon, D. J. Chem. Soc., Dalton Trans. 1972, 2526. (e) Cerveau, G.; Colomer, E.; Corriu, R. J. P.; Vioux, A. J. Organomet. Chem. 1987, 321 (3), 327. (f) Jesus, E.; Miguel, A. V.; Royo, P; Lanfredi, A. M. M.; Tiripicchio, A. J. Chem. Soc., Dalton Trans. 1990, 2779.
45. For leading references on a variety of transition-metal nitrosyl anions see: (a) Weiner, W. P.; Hollander, F. J.; Bergman, R. G. J. Am. Chem. Soc. 1984, 106, 7462. (b) Crocco, G. L.; Gladysz, J. A. J. Am. Chem. Soc. 1988, 110. 6110. (c) Weng, W.; Bartic, T.; Brady, M.; Bartik, B; Ramsden, J. A.; Arif, A. M.; Gladysz, J. A. J. Am. Chem. Soc. 1995, 117, 11922. (d) McCleverty, J. A.; Seddon, D. J. Chem. Soc., Dalton Trans. 1972, 2526. (e) Cerveau, G.; Colomer, E.; Corriu, R. J. P.; Vioux, A. J. Organomet. Chem. 1987, 321 (3), 327. (f) Jesus, E.; Miguel, A. V.; Royo, P; Lanfredi, A. M. M.; Tiripicchio, A. J. Chem. Soc., Dalton Trans. 1990, 2779.
46. For leading references on a variety of transition-metal nitrosyl anions see: (a) Weiner, W. P.; Hollander, F. J.; Bergman, R. G. J. Am. Chem. Soc. 1984, 106, 7462. (b) Crocco, G. L.; Gladysz, J. A. J. Am. Chem. Soc. 1988, 110. 6110. (c) Weng, W.; Bartic, T.; Brady, M.; Bartik, B; Ramsden, J. A.; Arif, A. M.; Gladysz, J. A. J. Am. Chem. Soc. 1995, 117, 11922. (d) McCleverty, J. A.; Seddon, D. J. Chem. Soc., Dalton Trans. 1972, 2526. (e) Cerveau, G.; Colomer, E.; Corriu, R. J. P.; Vioux, A. J. Organomet. Chem. 1987, 321 (3), 327. (f) Jesus, E.; Miguel, A. V.; Royo, P; Lanfredi, A. M. M.; Tiripicchio, A. J. Chem. Soc., Dalton Trans. 1990, 2779.
47. (a) Reference 8a, Chapter 4.
48. (b) Legzdins, P.; Wassink, B. Organometallics 1984, 3, 1811.