Abstract
The carbonylation of Os2(CO)10[μ-CH2N(Me)C(Et)](μ-H),1 at 110°C/1300 psi has yielded the carbene complex Os3(CO)11[C(Et)NMe2],2, the first simple carbene derivative of Os3(CO)12, in 68% yield. Compound2 was characterized by a single crystal structure analysis which showed the position of a dimethylaminocarbene ligand in an equatorial coordination site. Compound2 is decarbonylated at 97°C to reform1 in 59% yield. Compound1 can be decarbonylated further at 125°C to yield the new compound Os3(CO)9 [μ3-η2-C(H)N(Me)C(Et)](μ-H)2,3 in 94% yield. Compound3 was characterized by a crystal structure analysis and was shown to possess a triply bridging C(H)N(Me)C(Et) ligand containing two carbene centers. Compounds1 and2 can be regenerated from3 by carbonylation with CO at 110°C/800 psi. The facile activation of the N-methyl CH bonds of the carbene ligand of2 is produced by the metal atoms adjacent to the carbene coordination site, and may be a characteristic feature of the chemistry of carbene ligands in clusters. For2: space group=P\(\bar 1\),a=11.407(2) Å,b=12.332(2) Å,c=8.602(1) Å, α=103.92(1), β=110.56(1)°, γ=82.57(1),Z=2, 2627 reflections,R=0.031; for3: space group=C2/c,a=17.160(3) Å,b=8.947(2) Å,c=27.034(6) Å, β=97.82(1)°,Z=8, 2044 reflections,R=0.038.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
R. D. Adams (1989).Chem. Rev. 89, 1703.
K. H. Dötz, H. Fischer, P. Hofmann, F. R. Kreissel, U. Schubert, and K. Weiss (eds.),Transition Metal Carbene Complexes (Verlag Chemie, Weinheim, 1983).
H. D. Kaesz and C. M. Jensen (1988).Polyhedron 7, 1035.
R. D. Adams, inMetal-Metal Bonds and Clusters in Chemistry and Catalysis, J. P. Fackler, Jr. (Plenum, New York, 1990), pp. 75–89;
M. H. Chisholm, Ibid., pp. 55–74;
R. D. Adams and I. T. Horvath (1985).Prog. Inorg. Chem. 33, 127.
C. M. Jensen, T. J. Lynch, C. B. Knobler, and H. D. Kaesz (1982).J. Am. Chem. Soc. 104, 4679;
C. M. Jensen, C. B. Knobler, and H. D. Kaesz (1984).J. Am. Chem. Soc. 106, 5926.
R. D. Adams, G. Chen, and J. T. Tanner (1990).Organometallics 9, 1530.
R. D. Adams, G. Chen, J. T. Tanner, and J. Yin (1990).Organometallics 9, 1523.
R. D. Adams and G. Chen (1990).Organometallics 9, 2882.
International Tables for X-ray Crystallography (Kynoch Press: Birmingham, England, 1975), Vol. IV, Table 2.2B, pp. 99–101;
Ibid., Table 2.3.1, pp. 149–150.
B. G. DeBoer and M. R. Churchill (1977).Inorg. Chem. 16, 878.
R. D. Adams, J. E. Babin, and H. S. Kim (1987).J. Am. Chem. Soc. 109, 1414;
R. D. Adams, J. E. Babin, and H. S. Kim (1986).Inorg. Chem. 25, 4319.
U. Schubert,in K. H. Dötz, H. Fischer, P. Hofmann, F. R. Kreissel, U. Schubert, and K. Weiss (eds.),Transition Metal Carbene Complexes (Verlag-Chemie, Weinheim, 1983), p. 73.
M. R. Churchill,in R. Bau, (ed.),Transition Metal Hydrides (Adv. Chem. Ser. ACS No. 167, Washington, D.C., 1978).
C. M. Jensen and H. D. Kaesz (1987).J. Organomet. Chem. 330, 133.
J. P. Collman, L. S. Hegedus, J. R. Norton, and R. G. Finke,Principles and Applications of Organotransition Metal Chemistry (University Science Books, Mill Valley, California, 1987), Chap. 16.
R. D. Adams and G. Chen,Organometallics (in press).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Adams, R.D., Chen, G. Clusters containing carbene ligands. 12. The synthesis and transformations of Os3(CO)11[C(Et)NMe2], the first simple carbene derivative of Os3(CO)12 . J Clust Sci 2, 29–42 (1991). https://doi.org/10.1007/BF00702933
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF00702933