Isolation and characterization of the molybdenum alkylidyne complex [(F3C)Me2CO]2Mo(C-t-Bu)[N(Ar)P=C(H)(CMe 2Ph)] and its conversion to a phosphamolybdacyclobutene

Organometallics

Volumn 15, Issue 15, 1996, Pages 3244-3246

  Jamison, Gregory M ^a   Saunders, Randall S ^a   Wheeler, David R ^a   Alam, Todd M ^a   McClain, Mark D ^a   Loy, Douglas A ^a   Ziller, Joseph W ^b  

^a SANDIA NATIONAL LABORATORIES   (United States)

^b UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHARACTERIZATION; CHEMICAL REACTIONS; MOLECULAR STRUCTURE; SPECTROSCOPIC ANALYSIS; SYNTHESIS (CHEMICAL);

ISOLATION; MOLYBDENUM ALKYLIDYNES; PHOSPHAMOLYBDACYCLOBUTENES;

MOLYBDENUM COMPOUNDS;

EID: 0030197322     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om960418z     Document Type: Article

References (37)

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13. The isomeric mixture may be either an E/Z phosphaalkene mixture or perhaps rotamers about either Mo-N or N-P bonds.
14. Complete characterization and crystal structure details for 3b and 4b are provided in the Supporting Information.
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19. w = 0.114 for 4009 reflections with I > 2.0σ(I) and 416 parameters, GOF = 1.097.
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23. Alkynes: (a) Buhro, W. E.; Chisholm, M. H. Adv. Organomet. Chem. 1987, 27, 311. (b) Listemann, M. L.; Schrock, R. R. Organometallics 1985, 4, 74. Metal alkylidene catalyzed acetylene metathesis oligomerizations have been observed also: (c) Schlund, R.; Schrock, R. R.; Crowe, W. E. J. Am. Chem. Soc. 1989, 111, 8004. Nitriles: (d) Chisholm, M. H.; Folting-Streib, K.; Tiedtke, D. B.; Lemoigno, F.; Eisenstein, O. Angew. Chem., Int. Ed. Engl. 1995, 34, 110 and references cited therein.
24. Alkynes: (a) Buhro, W. E.; Chisholm, M. H. Adv. Organomet. Chem. 1987, 27, 311. (b) Listemann, M. L.; Schrock, R. R. Organometallics 1985, 4, 74. Metal alkylidene catalyzed acetylene metathesis oligomerizations have been observed also: (c) Schlund, R.; Schrock, R. R.; Crowe, W. E. J. Am. Chem. Soc. 1989, 111, 8004. Nitriles: (d) Chisholm, M. H.; Folting-Streib, K.; Tiedtke, D. B.; Lemoigno, F.; Eisenstein, O. Angew. Chem., Int. Ed. Engl. 1995, 34, 110 and references cited therein.
25. Alkynes: (a) Buhro, W. E.; Chisholm, M. H. Adv. Organomet. Chem. 1987, 27, 311. (b) Listemann, M. L.; Schrock, R. R. Organometallics 1985, 4, 74. Metal alkylidene catalyzed acetylene metathesis oligomerizations have been observed also: (c) Schlund, R.; Schrock, R. R.; Crowe, W. E. J. Am. Chem. Soc. 1989, 111, 8004. Nitriles: (d) Chisholm, M. H.; Folting-Streib, K.; Tiedtke, D. B.; Lemoigno, F.; Eisenstein, O. Angew. Chem., Int. Ed. Engl. 1995, 34, 110 and references cited therein.
26. Other examples of apparent phosphaacetylene metatheses with mononuclear alkylidynes include: (a) Hill, A. F.; Howard, J. A. K.; Spaniol, T. P.; Stone, F. G. A.; Szameitat, J. Angew. Chem., Int. Ed. Engl. 1989, 28, 210. (b) Hill, A. F. J. Mol. Catal. 1991, 65, 85. See ref 5 for reports of bimetallic complex mediated phosphaacetylene metatheses.
27. Other examples of apparent phosphaacetylene metatheses with mononuclear alkylidynes include: (a) Hill, A. F.; Howard, J. A. K.; Spaniol, T. P.; Stone, F. G. A.; Szameitat, J. Angew. Chem., Int. Ed. Engl. 1989, 28, 210. (b) Hill, A. F. J. Mol. Catal. 1991, 65, 85. See ref 5 for reports of bimetallic complex mediated phosphaacetylene metatheses.
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32. w = 0.106 for 2982 reflections with I > 2.0σ(I) and 415 parameters, GOF = 1.157.
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36. Neither an analogous transient nor 3a is observed in the reaction of 1a with 2. The electron-withdrawing bis(hexafluoro-tert-butoxy) substituents could activate reaction of an analogous transient too rapid to be observed on the NMR time scale.
37. It may be that the alkylidyne lies on the reaction coordinate between the reactants and the molybdacyclobutene. We are currently investigating both possibilities.