[en] Two new second generation ruthenium(11) dichloride-indenylidene complexes [RuCl2(9-isobutylphosphabicyclo[3.3.1]nonane)(NHC)(3-phenyl-1-indenylide ne)1, where NHC,3-bis(2,4,6-tri-methylphenyl)imidazolin-2-ylidene (SIMes) or its unsaturated imidazol-2-ylidene analogue (1Mes). were isolated in high yields upon heating a tetrahydrofuran (THF) solution of the diphosphane complex [RuCl2(isobutylphobane)2(3-phenyl-1-indenylidene)] with a two-fold excess of the corresponding imidazol(in)ium-2-carboxylate zwitterions. Both products were characterized by H-1, C-13, and P-33 NMR spectroscopy, and the molecular structure of [RuCl2(isobutylphobane)(SIMes)(3-phenyl-1-indenylidene)] was determined by X-ray diffraction analysis. A close inspection of the packing structure revealed the presence of different types of intra- and intermolecular interactions that enhanced the global stability of the crystals, while low temperature NMR experiments showed the existence of two distinct rotational isomers due to the unsymmetrical nature of the phobane ligand The catalytic activity of both compounds was assessed in olefin metathesis using
Disciplines :
Chemistry
Author, co-author :
Sauvage, Xavier ; Université de Liège - ULiège > Centre de recherches du cyclotron
Zaragoza, Guillermo
Demonceau, Albert ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie macromoléculaire et catalyse organique
Delaude, Lionel ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie macromoléculaire et catalyse organique
Language :
English
Title :
Mixed Isobutylphobane/N-Heterocyclic Carbene Ruthenium-Indenylidene Complexes: Synthesis and Catalytic Evaluation in Olefin Metathesis Reactions
a) R. H. Grubbs, S. J. Miller, G. C. Fu, Acc. Chem. Res. 1995, 28, 446-452
b) R. H. Grubbs, Tetrahedron 2004, 60, 7117-7140
c) R. H. Grubbs, Adv. Synth. Catal. 2007, 349, 34-40.
a) Handbook of Metathesis, (Ed.: R. H. Grubbs), Wiley-VCH, Weinheim, 2003
b)Green Metathesis Chemistry, (Eds.: V. Dragutan, A. Demonceau, I. Dragutan, E. S. Finkelshtein), NATO Science for Peace and Security Series - A: Chemistry and Biology, Springer, Dordrecht, 2010
c)Metathesis in Natural Product Synthesis: Strategies, Substrates and Catalysts, (Eds.: J. Cossy, S. Arseniyadis, C. Meyer), Wiley-VCH, Weinheim, 2010.
P. Schwab, M. B. France, J. W. Ziller, R. H. Grubbs, Angew. Chem. 1995, 107, 2179-2181
a) T. Weskamp, W. C. Schattenmann, M. Spiegler, W. A. Herrmann, Angew. Chem. 1998, 110, 2631 - 2633
Angew. Chem. Int. Ed. 1998, 37, 2490-2493
b) J. Huang, E. D. Stevens, S. P. Nolan, J. L. Petersen, J. Am. Chem. Soc. 1999, 121, 2674-2678
c) T. M. Trnka, J. P. Morgan, M. S. Sanford, T. E. Wilhelm, M. Scholl, T.-L. Choi, S. Ding, M.W. Day, R. H. Grubbs, J. Am. Chem. Soc. 2003, 125, 2546-2558
d) T. Ritter, M. W. Day, R. H. Grubbs, J. Am. Chem. Soc. 2006, 128, 11768-11769.
M. Scholl, S. Ding, C. W. Lee, R. H. Grubbs, Org. Lett. 1999, 1, 953-956.
a) J. S. Kingsbury, J. P. A. Harrity, P. J. Bonitatebus, Jr., A. H. Hoveyda, J. Am. Chem. Soc. 1999, 121, 791-799
b) S. B. Garber, J. S. Kingsbury, B. L. Gray, A. H. Hoveyda, J. Am. Chem. Soc. 2000, 122, 8168-8179
c) H. Wakamatsu, S. Blechert, Angew. Chem. 2002, 114, 832-834
a) Angew. Chem. Int. Ed. 2002, 41, 794-796
d) K. Grela, S. Harutyunyan, A. Michrowska, Angew. Chem. 2002, 114, 4210-4212
a) Angew. Chem. Int. Ed. 2002, 41, 4038-4040.
a) D. M. Lynn, B. Mohr, R. H. Grubbs, L. M. Henling, M. W. Day, J. Am. Chem. Soc. 2000, 122, 6601 - 6609
b) S. H. Hong, R. H. Grubbs, J. Am. Chem. Soc. 2006, 128, 3508-3509
c) A. Michrowska, Ł. Gułajski, Z. Kaczmarska, K. Mennecke, A. Kirschning, K. Grela, Green Chem. 2006, 8, 685-688
d) D. Burtscher, K. Grela, Angew. Chem. 2009, 121, 450-462
a)Angew. Chem. Int. Ed. 2009, 48, 442-454.
a) L. Jafarpour, M.-P. Heck, C. Baylon, H. M. Lee, C. Mioskowski, S. P. Nolan, Organometallics 2002, 21, 671-679
b) L. Yang, M. Mayr, K. Wurst, M. R. Buchmeiser, Chem. Eur. J. 2004, 10, 5761-5770
c) A. Michrowska, K. Mennecke, U. Kunz, A. Kirschning, K. Grela, J. Am. Chem. Soc. 2006, 128, 13261-13267
d) D. P. Allen, M. M. VanWingerden, R. H. Grubbs, Org. Lett. 2009, 11, 1261-1264
e) C. Che, W. Li, S. Lin, J. Chen, J. Zheng, J. Wu, Q. Zheng, G. Zhang, Z. Yang, B. Jiang, Chem. Commun. 2009, 5990-5992.
a) T. Ung, A. Hejl, R. H. Grubbs, Y. Schrodi, Organometallics 2004, 23, 5399-5401
b) A. Hejl, M. W. Day, R. H. Grubbs, Organometallics 2006, 25, 6149 - 6154;
c) S. Monsaert, A. Lozano Vila, R. Drozdzak, P. Vander Voort, F. Verpoort, Chem. Soc. Rev. 2009, 38, 3360-3372.
a) T. J. Seiders, D. W. Ward, R. H. Grubbs, Org. Lett. 2001, 3, 3225-3228
b) J. J. Van Veldhuizen, D. G. Gillingham, S. B. Garber, O. Kataoka, A. H. Hoveyda, J. Am. Chem. Soc. 2003, 125, 12502-12508
c) T. W. Funk, J. M. Berlin, R. H. Grubbs, J. Am. Chem. Soc. 2006, 128, 1840-1846.
For reviews, see: a) S. Beligny, S. Blechert, in: N-Heterocyclic Carbenes in Synthesis, (Ed.: S. P. Nolan), Wiley- VCH, Weinheim, 2006, pp 1 - 25
b) E. Despagnet- Ayoub, T. Ritter, in: N-Heterocyclic Carbenes in Transition Metal Catalysis, Topics in Organometallic Chemistry, Vol.21, (Ed.: F. Glorius), Springer, Berlin, 2007, pp 193 - 218
c) E. Colacino, J. Martinez, F. Lamaty, Coord. Chem. Rev. 2007, 251, 726-764
d) C. Samojłowicz, M. Bieniek, K. Grela, Chem. Rev. 2009, 109, 3708-3742
e) G. C. Vougioukalakis, R. H. Grubbs, Chem. Rev. 2010, 110, 1746-1787.
For reviews, see: a) C. E. Diesendruck, E. Tzur, N. G. Lemcoff, Eur. J. Inorg. Chem. 2009, 4185-4203
b) A. Lozano-Vila, S. Monsaert, A. Bajek, F. Verpoort, Chem. Rev. 2010, 110, in press (doi: 10.1021/cr900346r).
For reviews, see: a) V. Dragutan, I. Dragutan, F. Verpoort, Platinum Met. Rev. 2005, 49, 33-40
b) F. Boeda, H. Clavier, S. P. Nolan, Chem. Commun. 2008, 2726-2740.
a) M. Ulman, R. H. Grubbs, Organometallics 1998, 17, 2484-2489
b) M. S. Sanford, M. Ulman, R. H. Grubbs, J. Am. Chem. Soc. 2001, 123, 749-750
c) M. S. Sanford, J. A. Love, R. H. Grubbs, J. Am. Chem. Soc. 2001, 123, 6543-6554
d) J. A. Love, M. S. Sanford, M.W. Day, R. H. Grubbs, J. Am. Chem. Soc. 2003, 125, 10103-10109.
a) P. Schwab, R. H. Grubbs, J. W. Ziller, J. Am. Chem. Soc. 1996, 118, 100-110
b) E. L. Dias, S. T. Nguyen, R. H. Grubbs, J. Am. Chem. Soc. 1997, 119, 3887-3897.
a) A. Demonceau, A.W. Stumpf, E. Saive, A. F. Noels, Macromolecules 1997, 30, 3127-3136
b) D. Jan, L. Delaude, F. Simal, A. Demonceau, A. F. Noels, J. Organomet. Chem. 2000, 606, 55-64.
J. P. Mulders, (Shell International Research Maatschappij N. V.), Netherlands Patent 6604094, 1966.
a) G. Elsner, G. Heymer, H.-W. Stephan, (Hoechst A.G.), German Patent 2703802, 1978
b) A. J. Robertson, (Cytec Technology Corp.), World Patent 2000052017, 2000
c) P. N. Bungu, S. Otto, J. Organomet. Chem. 2007, 692, 3370-3379.
a) J. L. van Winkle, R. C. Morris, R. F. Mason, (Shell International Research Maatschappij N.V.), German Patent 1909620, 1969
b) P. W. N. M. van Leeuwen, Homogeneous Catalysis. Understanding the Art, Kluwer, Dordrecht, 2004, pp 125 - 138
c) P. N. Bungu, S. Otto, Dalton Trans. 2007, 2876-2884.
M. R. Eberhard, E. Carrington-Smith, E. E. Drent, P. S. Marsh, A. G. Orpen, H. Phetmung, P. G. Pringle, Adv. Synth. Catal. 2005, 347, 1345-1348.
a) J. C. Lewis, J. Y. Wu, R. G. Bergman, J. A. Ellman, Angew. Chem. 2006, 118, 1619-1621
a)Angew. Chem. Int. Ed. 2006, 45, 1589-1591
b) J. C. Lewis, A. M. Berman, R. G. Bergman, J. A. Ellman, J. Am. Chem. Soc. 2008, 130, 2493-2500.
J. Wolf, K. Thommes, O. Briel, R. Scopelliti, K. Severin, Organometallics 2008, 27, 4464-4474.
G. S. Forman, A. E. McConnell, M. J. Hanton, A. M. Z. Slawin, R. P. Tooze, W. J. van Rensburg, W. H. Meyer, C. Dwyer, M. M. Kirk, D. W. Serfontein, Organometallics 2004, 23, 4824-4827.
F. Boeda, H. Clavier, M. Jordaan, W. H. Meyer, S. P. Nolan, J. Org. Chem. 2008, 73, 259-263.
W. H. Meyer, M. M. D. Radebe, D. W. Serfontein, U. Ramdhani, M. du Toit, C. P. Nicolaides, Appl. Catal. A: Gen. 2008, 340, 236-241.
a) W. J. van Rensburg, P. J. Steynberg, M. M. Kirk, W. H. Meyer, G. S. Forman, J. Organomet. Chem. 2006, 691, 5312-5325
b) F. T. I. Marx, J. H. L. Joordan, H. C. M. Vosloo, J. Mol. Model. 2009, 15, 1371-1381.
G. S. Forman, A. E. McConnell, R. P. Tooze, W. J. van Rensburg, W. H. Meyer, M. M. Kirk, C. L. Dwyer, D. W. Serfontein, Organometallics 2005, 24, 4528-4542.
W. H. Meyer, A. E. McConnell, G. S. Forman, C. L. Dwyer, M. M. Kirk, E. L. Ngidi, A. Blignaut, D. Saku, A. M. Z. Slawin, Inorg. Chim. Acta 2006, 359, 2910-2917.
D. B. G. Williams, M. Ajam, A. Ranwell, Organometallics 2006, 25, 3088-3090.
S. Maechling, M. Zaja, S. Blechert, Adv. Synth. Catal. 2005, 347, 1413-1422.
G. S. Forman, R. M. Bellabarba, R. P. Tooze, A. M. Z. Slawin, R. Karch, R. Winde, J. Organomet. Chem. 2006, 691, 5513-5516.
X. Sauvage, A. Demonceau, L. Delaude, Adv. Synth. Catal. 2009, 351, 2031-2038.
For a recent review of the chemistry of betaine adducts of NHCs, see: L. Delaude, Eur. J. Inorg. Chem. 2009, 1681-1699.
For more detailed investigations on the thermal stability and decarboxylation of NHC·CO2 adducts, see: a) A. Tudose, A. Demonceau, L. Delaude, J. Organomet. Chem. 2006, 691, 5356-5365
b) H. Zhou, W.-Z. Zhang, C.-H. Liu, J.-P. Qu, X.-B. Lu, J. Org. Chem. 2008, 73, 8039-8044
c) B. R. Van Ausdall, J. L. Glass, K. M. Wiggins, A. M. Aarif, J. Louie, J. Org. Chem. 2009, 74, 7935-7942.
L. Jafarpour, H.-J. Schanz, E. D. Stevens, S. P. Nolan, Organometallics 1999, 18, 5416-5419.
D. Tapu, D. A. Dixon, C. Roe, Chem. Rev. 2009, 109, 3385-3407.
a) A. J. Arduengo, III, H. V. Rasika Dias, R. L. Harlow, M. Kline, J. Am. Chem. Soc. 1992, 114, 5530-5534;
b) A. J. Arduengo, III, R. Krafczyk, R. Schmutzler, H. A. Craig, J. R. Goerlich, W. J. Marshall, M. Unverzagt, Tetrahedron 1999, 55, 14523-14534
c) P. de Frémont, N. M. Scott, E. D. Stevens, S. P. Nolan, Organometallics 2005, 24, 2411-2418.
R. Dorta, E. D. Stevens, N. M. Scott, C. Costabille, L. Cavallo, C. D. Hoff, S. P. Nolan, J. Am. Chem. Soc. 2005, 127, 2485-2495.
M. Scholl, T. M. Trnka, J. P. Morgan, R. H. Grubbs, Tetrahedron Lett. 1999, 40, 2247-2250.
L. Jafarpour, A. C. Hillier, S. P. Nolan, Organometallics 2002, 21, 442-444.
S. Monsaert, R. Drozdzak, V. Dragutan, I. Dragutan, F. Verpoort, Eur. J. Inorg. Chem. 2008, 432-440.
H. Clavier, C. A. Urbina-Blanco, S. P. Nolan, Organometallics 2009, 28, 2848-2854.
For the complete 1H, 13C, and 31P NMR resonance assignments of various PCy3 or PPh3-based ruthenium-indenylidene complexes bearing NHC ligands, see: S. Monsaert, E. De Canck, R. Drozdzak, P. Van der Voort, F. Verpoort, J. C. Martins, P. M. S. Hendrickx, Eur. J. Org. Chem. 2009, 655-665.
a) A. Frstner, L. Ackermann, B. Gabor, R. Goddard, C. W. Lehmann, R. Mynott, F. Stelzer, O. R. Thiel, Chem. Eur. J. 2001, 7, 3236-3253
b) S. Prühs, C. W. Lehmann, A. Fürstner, Organometallics 2004, 23, 280-287
c) N. Ledoux, B. Allaert, S. Pattyn, H. Vander Mierde, C. Vercaemst, F. Verpoort, Chem. Eur. J. 2006, 12, 4654-4661
d) S. Leuthäusser, V. Schmidts, C. M. Thiele, H. Plenio, Chem. Eur. J. 2008, 14, 5465-5481.
C. L. Dwyer, M. M. Kirk, W. H. Meyer, W. J. van Rensburg, G. S. Forman, Organometallics 2006, 25, 3806-3812.
T. Ritter, A. Hejl, A. G. Wenzel, T. W. Funk, R. H. Grubbs, Organometallics 2006, 25, 5740-5745.
a) L. Delaude, M. Szypa, A. Demonceau, A. F. Noels, Adv. Synth. Catal. 2002, 344, 749-756
b) X. Sauvage, Y. Borguet, A. F. Noels, L. Delaude, A. Demonceau, Adv. Synth. Catal. 2007, 349, 255-265
c) X. Sauvage, Y. Borguet, G. Zaragoza, A. Demonceau, L. Delaude, Adv. Synth. Catal. 2009, 351, 441-455
d) L. Delaude, X. Sauvage, A. Demonceau, J. Wouters, Organometallics 2009, 28, 4056-4064.
H. Clavier, S. P. Nolan, Chem. Eur. J. 2007, 13, 8029-8036.
E. L. Dias, R. H. Grubbs, Organometallics 1998, 17, 2758-2767.
a) J. M. Berlin, K. Campbell, T. Ritter, T. W. Funk, A. Chlenov, R. H. Grubbs, Org. Lett. 2007, 9, 1339-1342
b) I. C. Stewart, T. Ung, A. A. Pletnev, J. M. Berlin, R. H. Grubbs, Y. Schrodi, Org. Lett. 2007, 9, 1589-1592
c) I. C. Stewart, C. J. Douglas, R. H. Grubbs, Org. Lett. 2008, 10, 441-444
d) I. C. Stewart, D. Benitez, D. J. O'Leary, E. Tkatchouk, M.W. Day, W. A. Goddard, III, R. H. Grubbs, J. Am. Chem. Soc. 2009, 131, 1931-1938.
a) V. Sashuk, L. H. Peeck, H. Plenio, Chem. Eur. J. 2010, 16, 3983-3993
b) X. Bantreil, R. A. M. Randall, A. M. Z. Slawin, S. P. Nolan, Organometallics 2010, 29, 3007-3011.
For a general discussion of selectivity in olefin crossmetathesis, see: A. K. Chatterjee, T.-L. Choi, D. P. Sanders, R. H. Grubbs, J. Am. Chem. Soc. 2003, 125, 11360-11370.
F. Boeda, X. Bantreil, H. Clavier, S. P. Nolan, Adv. Synth. Catal. 2008, 350, 2959-2966.
For theoretical studies, see: a) L. Cavallo, J. Am. Chem. Soc. 2002, 124, 8965-8973
b) S. F. Vyboishchikov, M. Bühl, W. Thiel, Chem. Eur. J. 2002, 8, 3962-3975
c) C. Adlhart, P. Chen, J. Am. Chem. Soc. 2004, 126, 3496-3510
d) B. Straub, Angew. Chem. 2005, 117, 6129-6132
a)Angew. Chem. Int. Ed. 2005, 44, 5974-5978
e) A. Correa, L. Cavallo, J. Am. Chem. Soc. 2006, 128, 13352-13353.
For a similar dichotomy between tricyclohexylphosphane- based complexes 3 and 4, see ref.[49]
G. Occhipinti, H.-R. Bjørsvik, V. R. Jensen, J. Am. Chem. Soc. 2006, 128, 6952-6964.
C. A. Tolman, Chem. Rev. 1977, 77, 313-348.
P. N. Bungu, S. Otto, Acta Crystallogr. 2009, E65, o560-o561.
A. Roodt, S. Otto, G. Steyl, Coord. Chem. Rev. 2003, 245, 121-137.
M. Carreira, M. Charernsuk, M. Eberhard, N. Fey, R. van Ginkel, A. Hamilton, W. P. Mul, A. G. Orpen, H. Phetmung, P. G. Pringle, J. Am. Chem. Soc. 2009, 131, 3078-3092.
a) M. Ulman, R. H. Grubbs, J. Org. Chem. 1999, 64, 7202-7207
b) S. H. Hong, M. W. Day, R. H. Grubbs, J. Am. Chem. Soc. 2004, 126, 7414-7415.
T. A. Kirkland, R. H. Grubbs, J. Org. Chem. 1997, 62, 7310-7318.
Bruker, APPEX II, Bruker AXS Inc., Madison, WI, USA, 2004.
P. T. Beurskens, G. Beurskens, R. de Gelder, J. M. M. Smits, S. Garcia-Granda, R. O. Gould, DIRDIF-2007, Radboud University: Nijmegen (The Netherlands), 2007.
G. M. Sheldrick, SHELX-97 (SHELXS 97 and SHELXL 97), Programs for Crystal Structure Analyses, University of Göttingen: G öttingen (Germany), 1998.
G. M. Sheldrick, SADABS, Programs for Scaling and Correction of Area Detection Data, University of Gottingen: Gottingen (Germany), 1996.