Journal of the American Chemical Society
Communication
(4) (a) Reithofer, M. R.; Schrock, R. R.; Muller, P. J. Am. Chem. Soc.
̈
data are all consistent with formation of 8c from structurally
characterized c,c,c-6c. Apparently three cis CC bonds between
C5 and C6 in each link in c,c,c-6c provide enough rigidity to allow
it to be crystallized readily.
The reaction between c,c,c-6c and (NMe2)3MoN (1.75
equiv) in C6D6 at 50 °C for 23 h led to the consumption of c,c,c-
6c and formation of 3 equiv of dimethylamine and a new C3-
symmetric Mo complex, according to NMR studies. The same is
true of the reaction between 8c and (NMe2)3MoN for 20 h.
Both reactions are qualitatively slower than analogous reactions
between 3c and (NMe2)3MoN (Scheme 2), as one might
expect. Unfortunately, no product has yet been isolated in
crystalline form.
We conclude that olefin metathesis can be employed to
prepare a TREN-derived macrocycle through intramolecular
RCM of 4c with WO-based catalyst 7, a highly Z-selective
catalyst for metathesis homocoupling of terminal olefins. The
optimum linkage contains 12 atoms between aryl rings and gives
rise to a 45 atom macrocyclic ring that contains all cis CC
bonds, c,c,c-6c. Hydrogenation of c,c,c-6c produces the saturated
version, 8c. It is clear that Mo can be reinserted into c,c,c-6c and
8c, although no nitrido complex has been isolated yet. Future
studies will be aimed at evaluating the chemistry of Mo
complexes that contain this and related macrocyclic TREN-
based ligands.
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ASSOCIATED CONTENT
* Supporting Information
■
S
Crystallographic details for all X-ray structural studies.
Experimental details for the synthesis of all organic and inorganic
compounds. This material is available free of charge via the
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AUTHOR INFORMATION
Corresponding Author
■
(16) (a) Fuller, A.-M.; Hughes, D. L.; Jones, G. A.; Lancaster, S. J.
Dalton Trans. 2012, 41, 5599. (b) Abram, U. Z. Anorg. Allg. Chem. 1999,
Notes
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625, 839−841. (c) Abram, U.; Kohl, F. J.; Ofele, K.; Herrmann, W. A.;
The authors declare no competing financial interest.
Voigt, A.; Kirmse, R. Z. Anorg. Allg. Chem. 1998, 624, 934. (d) Abram,
U.; Schmidt-Brucken, B.; Ritter, S. Polyhedron 1999, 18, 831. (e) Fox, A.
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ACKNOWLEDGMENTS
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R.; Cummins, C. C. J. Am. Chem. Soc. 2009, 131, 5716. (f) Crevier, T. J.;
Bennett, B. K.; Soper, J. D.; Bowman, J. A.; Dehestani, A.; Hrovat, D. A.;
Lovell, S.; Kaminsky, W.; Mayer, J. M. J. Am. Chem. Soc. 2001, 123, 1059.
We thank the Bill & Melinda Gates Foundation for past support
for catalytic dinitrogen reduction and the National Science
Foundation (CHE-1111133) for the work reported here. We
thank Li Li in the MIT DCIF for her assistance with mass
spectrometric sample analyses. The X-ray diffractometer was
purchased with the help of funding from the NSF under Grant
Number CHE-0946721.
(17) (a) Singh, R.; Schrock, R. R.; Muller, P.; Hoveyda, A. H. J. Am.
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