Synthesis and Organometallic Properties of Several Osmium Alkenylcarbyne Complexes

doi:10.6023/cjoc201305046

Abstract

Reactions of the dihydride complex OsH₂Cl₂(PCy₃)₂ (1) with HC≡CC(OH)Ph₂ at room temperature or under heating condition produce the hydride hydroxycarbyne complex OsHCl₂[≡CCH₂C(OH)Ph₂](PCy₃)₂ (2) and the hydride alkenylcarbyne complex OsHCl₂(≡CCH=CPh₂)(PCy₃)₂ (3), respectively. Treatment of 2 or 3 with HCl·Et₂O affords the trichlorocarbyne complex OsCl₃(≡CCH=CPh₂)(PCy₃)₂ (4), which can be conveniently synthesized by the one pot reaction of 1 with HC≡CC(OH)Ph₂ in the presence of HCl·Et₂O. Complex 4 can be alternatively prepared from the phosphine ligand substitution of the trichlorocarbyne complex OsCl₃(≡CCH=CPh₂)(PPh₃)₂ (5) with PCy₃, from which the mono-substituted intermediate OsCl₃(≡CCH=CPh₂)(PCy₃)(PPh₃) (6) can be isolated. Complex 4 undergoes ligand substitution reactions with water and pyridine leading to the formation of the aqua and pyridine-coordinate mono phosphine carbyne complexes OsCl₃(≡CCH=CPh₂)(PCy₃)(S) (S=H₂O, 7; S=Py, 8). In addition, complex 4 reacts with NaOEt at room temperature to produce the alkenylcarbene complex OsCl₂(=CHCH=CPh₂)(PCy₃)₂ (9), which is unstable in solution and evolves into the thermally more stable hydride carbyne complex 3. In contrast, the reaction of 4 with EtOH can only take place at elevated temperature to give the hydride carbyne 3.

Key words: osmium, carbyne, carbene, terminal alkyne, hydride complex

Cite this article

An Ran, Li Ting, Wen Ting-Bin. Synthesis and Organometallic Properties of Several Osmium Alkenylcarbyne Complexes[J]. Chin. J. Org. Chem., 2013, 33(08): 1697-1708.

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References

[1] For general reviews on the chemistry of transition metal carbyne complexes see:
(a) Kim H. P.; Angelici, R. J. Adv. Organomet. Chem. 1987, 27, 51.
(b) Fischer, H.; Hofmann, P.; Kreissl, F. R.; Schrock, R. R.; Schubert, U.; Weiss, K. In Carbyne Complexes, VCH, Weinheim, Germany, 1988.
(c) Maya, A.; Hoffmeister, H. Adv. Organomet. Chem. 1991, 32, 227.
(d) Engel, P. F.; Pfeffer, M. Chem. Rev. 1995, 95, 2281.
(e) Schrock, R. R. Chem. Rev. 2002, 102, 145.
(f) Schrock, R. R. Chem. Commun. 2005, 2773.
[2] For selective reviews on alkyne metathesis see:
(a) Fürstner, A. Angew. Chem., Int. Ed. 2013, 52, 2794.
(b) Schrock, R. R.; Czekelius, C. Adv. Synth. Catal. 2007, 349, 55.
(c) Schrock, R. R. Angew. Chem., Int. Ed. 2006, 45, 3748.
(d) Zhang, W.; Moore, J. S. Adv. Synth. Catal. 2007, 349, 93.
(e) Fürstner, A.; Davies, P. W. Chem. Commun. 2005, 2307.
[3] (a) Schrock, R. R.; Clark, D. N.; Sancho, J.; Wengrovius, J. H.; Rocklage, S. M.; Pdersen, S. F. Organometallics 1982, 1, 1645.
(b) Wengrovius, J. H.; Sancho, J.; Schrock, R. R. J. Am. Chem. Soc. 1981, 103, 3932.
[4] (a) Zhang, W.; Moore, J. S. J. Am. Chem. Soc. 2005, 127, 11863.
(b) Weissman, H.; Plunkett, K. N.; Moore, J. S. Angew. Chem., Int. Ed. 2006, 45, 585.
[5] (a) Hickmann, V.; Alcarazo, M.; Fürstner, A. J. Am. Chem. Soc. 2010, 132, 11042.
(b) Heppekausen, J.; Stade, R.; Goddard, R.; Fürstner, A. J. Am. Chem. Soc. 2010, 132, 11045.
[6] Bunz, H. F. Acc. Chem. Res. 2001, 34, 998.
[7] (a) Vougioukalakis, G. C.; Grubbs, R. H. Chem. Rev. 2010, 110, 1746.
(b) Grubbs, R. H. Angew. Chem., Int. Ed. 2006, 45, 3760.
(c) Grubbs, R. H. Tetrahedron 2004, 60, 7117.
(d) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18.
[8] (a) Villar, H.; Frings, M.; Bolm, C. Chem. Soc. Rev. 2007, 36, 55.
(b) Compain P. Adv. Synth. Catal. 2007, 349, 1829.
(c) Deiters, A.; Martin, S. F. Chem. Rev. 2004, 104, 2199.
(d) Fürstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012.
[9] For reviews on osmium carbyne complexes see:
(a) Gallop, M. A.; Roper, W. R. Adv. Organomet. Chem. 1986, 25, 121.
(b) Roper, W. R. In Transition Metal Carbyne Complexes, Ed.: Kreissl, F. R., Kluwer Academic, Dordrecht, The Netherlands, 1993, 155.
(c) Jia, G. Coord. Chem. Rev. 2007, 251, 2167.
(d) Bolaño, T.; Esteruelas, M. A.; Oñate, E. J. Organomet. Chem. 2011, 696, 3911.
[10] Clark, G. R.; Marsden, K.; Roper, W. R.; Wright, L. J. J. Am. Chem. Soc. 1980, 102, 6570.
[11] Selected recent examples of osmium carbyne complexes:
(a) Chen, J.; Shi, C.; Sung, H. H. Y.; Williams, I. D.; Lin, Z.; Jia, G. Angew. Chem., Int. Ed. 2011, 50, 7295.
(b) Castro-Rodrigo, R.; Esteruelas, M. A.; López, A. M.; Mozo, S.; Oñate, E. Organometallics 2010, 29, 4071.
(c) Richter, B.; Werner, H. Organometallics 2009, 28, 5137.
(d) Bolaño, T.; Alba Collado, A.; Esteruelas, M. A.; Oñate, E. Organometallics 2009, 28, 2107.
(e) Buil, M. L.; Esteruelas, M. A.; Garcés, K.; Oliván, M.; Oñate, E. Organometallics 2008, 27, 4680.
(f) Castro-Rodrigo, R.; Esteruelas, M. A.; López, A. M.; Oñate, E. Organometallics 2008, 27, 3547.
(g) Castarlenas, R.; Esteruelas, M. A.; Lalrempuia, R.; Oliván, M.; Oñate, E. Organometallics 2008, 27, 795.
(h) Lee, J. H.; Pink, M.; Smurnyy, Y. D.; Caulton, K. G. J. Organomet. Chem. 2008, 693, 1426.
(i) He, G.; Zhu, J.; Hung, W. Y.; Wen, T. B.; Sung, H. H. Y.; Williams, I. D.; Lin, Z.; Jia, G. Angew. Chem., Int. Ed. 2007, 46, 9065.
(j) Lee, J. H.; Pink, M.; Caulton, K. G. Organometallics 2006, 25, 802.
(k) Esteruelas, M. A.; González, A. I.; López, A. M.; Oñate, E. Organometallics 2004, 23, 4858.
(l) Barrio, P.; Esteruelas, M. A.; Oñate, E. J. Am. Chem. Soc. 2004, 126, 1946.
(m) Barrio, P.; Esteruelas, M. A.; Oñate, E. Organometallics 2003, 22, 2472.
(n) Weberndörfer, B.; Henig, G.; Hockless, D. C. R.; Bennett, M. A.; Werner, H. Organometallics 2003, 22, 744.
(o) Esteruelas, M. A.; López, A. M.; Oñate, E.; Royo, E. Organometallics 2004, 23, 3021.
(p) Castarlenas, R.; Esteruelas, M. A.; Oñate, E. Organometallics 2001, 20, 3283.
(q) Buil, M. L.; Esteruelas, M. A.; Garc韆-Yebra, C.; Gutiérrez-Puebla, E.; Oliván, M. Organometallics 2000, 19, 2184.
(r) Wen, T. B.; Cheung, Y. K.; Yao, J.; Wong, W. T.; Zhou, Z. Y.; Jia, G. Organometallics 2000, 19, 3803.
[12] Espuelas, J.; Esteruelas, M. A.; Lahoz, F. J.; Oro, L. A.; Ruiz, N. J. Am. Chem. Soc. 1993, 115, 4683.
[13] Buil, M. L.; Esteruelas, M. A.; Garcés, K.; Oñate, E. Organometallics 2009, 28, 5691.
[14] Collado, A.; Esteruelas, M. A.; López, F.; Mascareñas, J. L.; Oñate, E.; Trillo, B. Organometallics 2010, 29, 4966.
[15] Collado, A.; Esteruelas, M. A.; Oñate, E. Organometallics 2011, 30, 1930.
[16] Spivak, G. J.; Coalter, J. N.; Olivan, M.; Eisenstein, O.; Caulton, K. G. Organometallics 1998, 17, 999.
[17] Ferrando, G.; Coalter, J. N.; Gerard, H.; Huang, D.; Eisenstein, O.; Caulton, K. G. New J. Chem. 2003, 27, 1451.
[18] (a) Liu, B.; Xie, H.; Wang, H.; Wu, L.; Zhao, Q.; Chen, J.; Wen, T. B.; Cao, Z.; Xia, H. Angew. Chem., Int. Ed. 2009, 48, 5461.
(b) Liu, B.; Xie, H.; Wang, H.; Wu, L.; Zeng, B.; Chen, J.; Tao, J.; Wen, T. B.; Cao, Z.; Xia, H. Angew. Chem., Int. Ed. 2009, 48, 5430.
[19] Werner, H.; Jung, S.; Weberndorfer, B.; Wolf, J. Eur. J. Inorg. Chem. 1999, 951.
[20] Castarlenas, R.; Esteruelas, M. A.; Oñate, E. Organometallics 2007, 26, 2129.
[21] Bolaño, T.; Castarlenas, R.; Esteruelas, M. A.; Modrego, F. J.; Oñate, E. J. Am. Chem. Soc. 2005, 127, 11184.
[22] (a) Wen, T. B.; Hung, W. Y.; Zhou, Z. Y.; Lo, M. F.; Williams, I. D.; Jia, G. Eur. J. Inorg. Chem. 2004, 2837.
(b) Wen, T. B.; Zhou, Z. Y.; Lo, M. F.; Williams, I. D.; Jia, G. Organometallics 2003, 22, 5217.
[23] Bolaño, T.; Castarlenas, R.; Esteruelas, M. A.; Oñate, E. Organometallics 2007, 26, 2037.
[24] Stewart, M. H.; Johnson, M. J.; Kampf, J. W. Organometallics 2007, 26, 5102.
[25] (a) Crochet, P.; Esteruelas, M. A.; López, A. M.; Martinez, M. P.; Oliván, M.; Oñate, E.; Ruiz, N. Organometallics 1998, 17, 4500.
(b) Esteruelas, M. A.; Oliván, M.; Oñate, E. Organometallics 1999, 18, 2953.
(c) Bustelo, E.; Jiménez-Tenorio, M.; Mereiter, K.; Puerta, M. C.; Valerga, P. Organometallics 2002, 21, 1903.
(d) Esteruelas, M. A.; González, A. I.; López, A. M.; Oñate, E. Organometallics 2003, 22, 414;
[26] Chen, J. X.; Sung, H. H. Y.; Williams, I. D.; Jia, G. Organometallics 2011, 30, 6159.
[27] (a) Bruce, M. I. Chem. Rev. 1991, 91, 197.
(b) Bruce, M. I. Chem. Rev. 1998, 98, 2797.
[28] Nickias, P. N.; Selegue, J. P.; Young, B. A. Organometallics 1998, 7, 2248.
[29] Kuhlman, R. Coord. Chem. Rev. 1997, 167, 205.
[30] (a) Quagliano, J. V.; Schubert, L. Chem. Rev. 1952, 50, 201.
(b) Coe, B. J.; Glenwright, S. J. Coord. Chem. Rev. 2000, 203, 5.
[31] Shaffer, E. A.; Chen, C. L.; Beatty, A. M.; Schanz, H. J. J. Organomet. Chem. 2007, 692, 5221.
[32] (a) Baya, M.; Crochet, P.; Esteruelas, M. A.; Gutiérrez-Puebla, E.; López, A. M.; Modrego, J.; Oñate, E.; Vela, N. Organometallics 2000, 19, 2585.
(b) Bolaño, T.; Castarlenas, R.; Esteruelas, M. A.; Oñate, E. J. Am. Chem. Soc. 2006, 128, 3965.
[33] Nguyne, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1993, 115, 9858.
[34] (a) Nguyne, S. T.; Johnson, L. K.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 3974.
(b) Schwab P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100.
[35] (a) Caulton, K. G. J. Organomet. Chem. 2011, 617, 56.
(b) Esteruelas, M. A.; Oro, L. A. Adv. Organomet. Chem. 2001, 47, 1.
(c) Esteruelas, M. A.; López, A. M.; Oliván, M. Coord. Chem. Rev. 2007, 251, 795.

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