Reversible C-H bond activation in coordinatively unsaturated molybdenum aryloxy complexes, Mo(PMe3)4(OAr)H: Comparison with their tungsten analogs

Organometallics

Volumn 15, Issue 19, 1996, Pages 3910-3912

  Hascall, Tony ^a   Murphy, Vincent J ^a   Parkin, Gerard ^a  

^a Teachers College   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000630499     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om960553b     Document Type: Review

References (33)

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10. 2 See: Jang, S.; Atagi, L. M.; Mayer, J. M. J. Am. Chem. Soc. 1990, 112, 6413-6414.
11. 2)H is orthorhombic, Pnma (No. 62), with a = 20.055(5) Å, b = 17.076(5) Å, c = 9.400(3) Å, and Z = 4.
12. 6a For reference, the mean Mo-OAr bond length for complexes listed in the Cambridge Structural Database (version 5.11) is 1.99 Å. See, for example: (a) Bartos, M. J.; Kriley, C. E.; Yu. J. S.; Kerschner, J. L.; Fanwick, P. E.; Rothwell, I. P. Polyhedron 1989, 8, 1971-1977. (b) Kerschner, J. L.; Yu, J. S.; Fanwick, P. E.; Rothwell, I. P.; Huffman, J. C. Organometallics 1989, 8, 1414-1418. (c) Walborsky, E. C.; Wigley, D. E.; Roland, E.; Dewan, J. C.; Schrock, R. R. Inorg. Chem. 1987, 26, 1615-1621. (d) Kerschner, J. L.; Torres, E. M.; Fanwick, P. E.; Rothwell, I. P.; Huffman, J. C. Organometallics 1989, 8, 1424-1431.
13. 6a For reference, the mean Mo-OAr bond length for complexes listed in the Cambridge Structural Database (version 5.11) is 1.99 Å. See, for example: (a) Bartos, M. J.; Kriley, C. E.; Yu. J. S.; Kerschner, J. L.; Fanwick, P. E.; Rothwell, I. P. Polyhedron 1989, 8, 1971-1977. (b) Kerschner, J. L.; Yu, J. S.; Fanwick, P. E.; Rothwell, I. P.; Huffman, J. C. Organometallics 1989, 8, 1414-1418. (c) Walborsky, E. C.; Wigley, D. E.; Roland, E.; Dewan, J. C.; Schrock, R. R. Inorg. Chem. 1987, 26, 1615-1621. (d) Kerschner, J. L.; Torres, E. M.; Fanwick, P. E.; Rothwell, I. P.; Huffman, J. C. Organometallics 1989, 8, 1424-1431.
14. 6a For reference, the mean Mo-OAr bond length for complexes listed in the Cambridge Structural Database (version 5.11) is 1.99 Å. See, for example: (a) Bartos, M. J.; Kriley, C. E.; Yu. J. S.; Kerschner, J. L.; Fanwick, P. E.; Rothwell, I. P. Polyhedron 1989, 8, 1971-1977. (b) Kerschner, J. L.; Yu, J. S.; Fanwick, P. E.; Rothwell, I. P.; Huffman, J. C. Organometallics 1989, 8, 1414-1418. (c) Walborsky, E. C.; Wigley, D. E.; Roland, E.; Dewan, J. C.; Schrock, R. R. Inorg. Chem. 1987, 26, 1615-1621. (d) Kerschner, J. L.; Torres, E. M.; Fanwick, P. E.; Rothwell, I. P.; Huffman, J. C. Organometallics 1989, 8, 1424-1431.
15. 6a For reference, the mean Mo-OAr bond length for complexes listed in the Cambridge Structural Database (version 5.11) is 1.99 Å. See, for example: (a) Bartos, M. J.; Kriley, C. E.; Yu. J. S.; Kerschner, J. L.; Fanwick, P. E.; Rothwell, I. P. Polyhedron 1989, 8, 1971-1977. (b) Kerschner, J. L.; Yu, J. S.; Fanwick, P. E.; Rothwell, I. P.; Huffman, J. C. Organometallics 1989, 8, 1414-1418. (c) Walborsky, E. C.; Wigley, D. E.; Roland, E.; Dewan, J. C.; Schrock, R. R. Inorg. Chem. 1987, 26, 1615-1621. (d) Kerschner, J. L.; Torres, E. M.; Fanwick, P. E.; Rothwell, I. P.; Huffman, J. C. Organometallics 1989, 8, 1424-1431.
16. See Supporting Information.
17. 3.
18. The location of the hydride ligands were observed in electron density difference maps; however, as with most hydrides coordinated to heavy metals, their location as determined by X-ray diffraction is subject to considerable uncertainty.
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22. P-H = 47 Hz. See: Henderson, R. A.; Hughes, D. L.; Richards, R. L.; Shortman, C. J. Chem. Soc., Dalton Trans. 1987, 1115-1121.
23. 2 (e.g. X = Cl, I). See ref 3b and: Carmona, E.; Marín, J. M.; Poveda, M. L.; Atwood, J. L.; Rogers, R. D. Polyhedron 1983, 2, 185-193.
24. Rothwell has also noted a correlation between electron count and W-OAr bond length in a series of tungsten aryloxide complexes. See: Kerschner, J. L.; Fanwick, P. E.; Rothwell, I. P. Inorg. Chem. 1989, 28, 780-786.
25. 2)H are 159.7(3) and 145.9(6)°, respectively; however it should be noted that on its own such a parameter cannot be reliably used as an indicator of π-bonding. See ref 14 and: (a) Howard, W. A.; Trnka, T. M.; Parkin, G. Inorg. Chem. 1995, 34, 5900-5909. (b) Steffey, B. D.; Fanwick, P. E.; Rothwell, I. P. Polyhedron 1990, 9, 963-968. (c) Coffindaffer, T. W.; Steffy, B. D.; Rothwell, I. P.; Folting, K.; Huffman, J. C.; Streib, W. E. J. Am. Chem. Soc. 1989, 111, 4742-4749.
26. 2)H are 159.7(3) and 145.9(6)°, respectively; however it should be noted that on its own such a parameter cannot be reliably used as an indicator of π-bonding. See ref 14 and: (a) Howard, W. A.; Trnka, T. M.; Parkin, G. Inorg. Chem. 1995, 34, 5900-5909. (b) Steffey, B. D.; Fanwick, P. E.; Rothwell, I. P. Polyhedron 1990, 9, 963-968. (c) Coffindaffer, T. W.; Steffy, B. D.; Rothwell, I. P.; Folting, K.; Huffman, J. C.; Streib, W. E. J. Am. Chem. Soc. 1989, 111, 4742-4749.
27. 2)H are 159.7(3) and 145.9(6)°, respectively; however it should be noted that on its own such a parameter cannot be reliably used as an indicator of π-bonding. See ref 14 and: (a) Howard, W. A.; Trnka, T. M.; Parkin, G. Inorg. Chem. 1995, 34, 5900-5909. (b) Steffey, B. D.; Fanwick, P. E.; Rothwell, I. P. Polyhedron 1990, 9, 963-968. (c) Coffindaffer, T. W.; Steffy, B. D.; Rothwell, I. P.; Folting, K.; Huffman, J. C.; Streib, W. E. J. Am. Chem. Soc. 1989, 111, 4742-4749.
28. (a) Bonding Energetics in Organometaliic Compounds; Marks, T. J., Ed.; ACS Symposium Series; American Chemical Society: Washington, DC, 1990; Vol. 428.
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31. (d) Skinner, H. A.; Connor, J. A. Pure Appl. Chem. 1985, 57, 79-88.
32. It must also be recognized that the oxidative addition of the C-H bond will be accompanied by loss of oxygen to metal π-donation.
33. 2. See: Rabinovich, D.; Parkin, G. J. Am. Chem. Soc. 1993, 115, 353-354.