Inorganic Chemistry
Article
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metallics 2004, 23, 3425. (f) Cadierno, V.; Díez, J.; García-Alvarez, J.;
Gimeno, J.; Nebra, N.; Rubio-García, J. Dalton Trans. 2006, 5593.
García-Garrido, S. E.; Gimeno, J. Dalton Trans. 2010, 39, 4015.
(c) Bauer, E. B. Synthesis 2012, 44, 1131.
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(24) High-oxidation state rhenium complexes have been previously
described as efficient catalysts for the isomerization of propargylic
alcohols into α,β-unsaturated carbonylic compounds in conventional
organic solvents in: (a) Narasaka, K.; Kusama, H.; Hayashi, Y. Chem.
Lett. 1991, 1413. (b) Narasaka, K.; Kusama, H.; Hayashi, Y.
Tetrahedron 1992, 48, 2059. (c) Lorber, C. Y.; Osborn, J. A.
Tetrahedron Lett. 1996, 37, 853. (d) Sherry, B. D.; Radosevich, A. T.;
Toste, F. D. J. Am. Chem. Soc. 2003, 125, 6076. (e) Luzun, M. R.;
Toste, F. D. J. Am. Chem. Soc. 2003, 125, 15760. (f) Trost, B. M.;
Chung, C. K. J. Am. Chem. Soc. 2006, 128, 10358. (g) Stefanoni, M.;
Luparia, M.; Porta, A.; Zanoni, G.; Vidari, G. Chem.Eur. J. 2009, 15,
3940. (h) Nolin, K. A.; Ahn, R. W.; Kobayashi, Y.; Kennedy-Smith, J.
J.; Toste, F. D. Chem.Eur. J. 2010, 16, 9555. (i) Saito, K.; Onizawa,
Y.; Iwasawa, N. Chem.Eur. J. 2010, 16, 4716. (j) Mattia, E.; Porta,
A.; Merlini, V.; Zanoni, G.; Vidari, G. Chem.Eur. J. 2012, 18, 11894.
(25) Sarma, R.; Prajapati, D. Synlett 2008, 3001.
(26) We have investigated the Meyer−Schuster rearrangement of the
alkynol 7a using the ionic liquid [BMIM][BF4] as a solvent. However,
longer reaction time was required (5 h, 95% yield). It is also important
to note that in the absence of the rhenium(I) catalyst the reaction did
not generate any product.
(27) Such an E-selectivity with secondary alkynols has been
previously observed in some catalytic systems, see for example:
(a) Cadierno, V.; García-Garrido, S. E.; Gimeno, J. Adv. Synth. Catal.
2006, 348, 101. (b) Cadierno, V.; Francos, J.; Gimeno, J. Tetrahedron
Lett. 2009, 50, 4773. (c) Cadierno, V.; Gimeno, J.; Nebra, N.
ChemCatChem 2010, 2, 519. (d) Cadierno, V.; García-Garrido, S. E.;
(g) Cadierno, V.; Díez, J.; García-Alvarez, J.; Gimeno, J.; Rubio-García,
J. Dalton Trans. 2008, 5737.
(7) Advanced Inorganic Chemistry, 6th ed.; Cotton, F. A., Wilkinson,
G., Murillo, C. A., Bochmann, M., Eds.; Wiley Interscience: New York,
1999.
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(8) García-Alvarez, J.; Díez, J.; Gimeno, J.; Seifried, C. M. Chem.
Commun. 2011, 47, 6470.
(9) As far as we are aware, there is only one further example of a
tricarbonyl Re(I) derivative containing an iminophosphorane-
phosphine ligand (PPh2CH2P(NH)Ph2) in: (a) Hagenbach, A.;
Athenstaedt, S.; Daroczi, H. E.; Abram, U.; Alberto, R. Z. Anorg. Allg.
Chem. 2004, 630, 2709. For other Re(V) complexes containing
iminophosphorane-phosphine ligands, see: (b) Katti, K. V.; Cavell, R.
G. Inorg. Chem. 1989, 28, 3033. Also see: (c) Hecht, M.; Saucedo
Anaya, S.; Hagenbach, A.; Abram, U. Inorg. Chem. 2005, 44, 3172.
(10) (a) Meyer, K. H.; Schuster, K. Ber. Dtsch. Chem. Ges. 1922, 55,
819. (b) Rupe, H.; Kambli, E. Helv. Chim. Acta 1926, 9, 672.
(11) A similar mixture of κ2-P,O- and κ2-P,N-coordination modes of
ligand 1a in an arene−Ru(II) fragment has been previously described
by us in ref 6c.
(12) We have previously reported the selective S-coordination of the
N-thiophosphoryl-iminophosphoranyl fragment in Ru(II) centers, see
ref 6d.
(13) We have previously reported the coordination of the
iminophosphorane-phosphine ligands 1e−g in Ru(II) fragments in:
Cadierno, V.; Díez, J.; García-Alvarez, J.; Gimeno, J. Chem. Commun.
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2004, 1820. See also refs 6a and 6b.
Gimeno, J.; Nebra, N. Inorg. Chim. Acta 2010, 50, 1912. (e) Antinolo,
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(14) (a) Larre, C.; Donnadieu, B.; Caminade, A.-M.; Majoral, J. P.
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A.; Carrillo-Hermosilla, F.; Cadierno, V.; García-Alvarez, J.; Otero, A.
Chem.Eur. J. 1998, 4, 2031. (b) Rossell, O.; Seco, M.; Caminade, A.-
M.; Majoral, J. P. Gold Bull. 2001, 34, 88. (c) Turrin, B.; Donnadieu,
B.; Caminade, A.-M.; Majoral, J. P. Z. Anorg. Allg. Chem. 2005, 631,
2881. (d) Maraval, A.; Magro, G.; Maraval, V.; Vendier, L.; Caminade,
A.-M.; Majoral, J. P. J. Organomet. Chem. 2006, 691, 1333.
ChemCatChem 2012, 4, 123. See also refs 24g and 24j.
(28) Recoverable and Recyclable Catalyst; Benaglia, M., Ed.; John
Wiley & Sons: Chichester, U. K., 2009.
(29) By monitoring the catalytic isomerization of propargylic alcohols
9 into enones 10 by GC/MS, the intermediate formation of the
corresponding terminal 1,3-enynes HCC−C(R′)CR2 was
observed. Unfortunately, all attempts to prevent the subsequent
hydration step were unsuccessful disabling the selective synthesis of
the 1,3-enynes.
(30) It is well-known that low-oxidation Re(I) carbonyl fragments are
able to activate terminal propargylic alcohols, for example, see:
(a) Bianchini, C.; Mantovani, N.; Marvelli, L.; Peruzzini, M.; Rossi, R.;
Romerosa, A. J. Organomet. Chem. 2001, 617−618, 233. (b) Mantovani,
N.; Marvelli, L.; Rossi, R.; Bianchini, C.; de los Rios, I.; Romerosa, A.;
Peruzzini, M. J. Chem. Soc., Dalton Trans. 2001, 2353. (c) Coletti, C.;
Gonsalvi, L.; Guerriero, A.; Marvelli, L.; Peruzzini, M.; Reginato, G.;
Re, N. Organometallics 2012, 31, 57.
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(15) Cadierno, V.; Díez, J.; García-Alvarez, J.; Gimeno, J. Dalton
Trans. 2007, 2760.
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(16) (a) García-Alvarez, J.; Díez, J.; Gimeno, J. Green Chem. 2010, 12,
2127. (b) García-Alvarez, J.; Díez, J.; Gimeno, J.; Suarez, F. J.; Vicent,
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C. Eur. J. Inorg. Chem. 2012, 5854.
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(17) (a) Cadierno, V.; Díez, J.; García-Alvarez, J.; Gimeno, J.
Organometallics 2008, 27, 1809. (b) Cadierno, V.; Díez, J.; García-
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Alvarez, J.; Gimeno, J. Dalton Trans. 2010, 39, 941.
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(18) García-Alvarez, J.; Díez, J.; Vidal, C. Green Chem. 2012, 14,
3190.
(19) Synthesis, multinuclear NMR spectra, and IR data for complex
4d have been reported by us in ref 8.
(31) For a recent book covering the synthesis, reactivity, and catalytic
applications of transition-metal vinylidenes and allenylidene com-
plexes, see: Metal Vinylidenes and Allenylidenes in Catalysis: From
Reactivity to Applications in Synthesis; Bruneau, C., Dixneuf, P. H., Eds.;
Wiley-VCH: Weinheim, Germany, 2008.
(20) Similar hemilabile behavior was previously described by us in
arene−ruthenium(II) complexes containing ligand 1b, see ref 6c.
(21) (a) Chan, L. Y. Y.; Isaacs, E. E.; Graham, W. A. G. Can. J. Chem.
1977, 55, 111. (b) Kabir, S. E.; Ahmed, F.; Ghosh, S.; Hassan, M. R.;
Islam, M. S.; Sharmin, A.; Tocher, D. A.; Haworth, D. T.; Lindeman, S.
V.; Siddiquee, T. A.; Bennett, D. W.; Hardcastle, K. I. J. Organomet.
Chem. 2008, 693, 2657.
(32) Fristch, E.; Kerscher, T.; Polborn, K.; Beck, W. J. Organomet.
Chem. 1993, 460, C25.
(33) Although a dehydration/hydration sequence through a
carbocation for isomerization of propargylic alcohols cannot be
discarded, usually harsh reactions conditions and strong acidic media
are required (see ref 23).
(22) (a) Handbook of Green Chemistry; Wiley-VCH: Weinheim,
Germany, 2011; Vols.: 4, 5, and 6, Green Solvents (Anastas, P. T.,
Ed.); Vol. 4: Supercritical Solvents (Leitner, W., Jessop, P. G., Eds.);
Vol. 5: Reactions in Water (Li, C.-J., Ed.); Vol. 6: Ionic Liquids
(34) 31P{1H} NMR spectrum of the crude mixture after the catalytic
reaction confirms the presence of the complex 4d in the catalytic
medium.
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(Wasserschied, P., Stark, A., Eds.). (b) Díaz-Alvarez, A. E.; Francos, J.;
Lastra-Barreira, B.; Crochet, P.; Cadierno, V. Chem. Commun. 2011,
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47, 6208. (c) Díaz-Alvarez, A. E.; García-Alvarez, R.; Crochet, P.;
Cadierno, V. In Glycerol: Production, Structure and Applications; De
Santos Silva, M., Costa Ferreira, P., Eds.; Nova Publishers: Hauppauge,
New York, 2012.
(35) Schmidt, S. P.; Trogler, W. C.; Basolo, F. Inorg. Synth. 1990, 28,
160.
(36) Midland, M. M. J. Org. Chem. 1975, 40, 2250.
(23) For recent review articles on this catalytic process including
catalysts presently available, their mechanisms of action, as well as
relevant synthetic applications, see: (a) Engel, D. A.; Dudley, G. B.
Org. Biomol. Chem. 2009, 7, 4149. (b) Cadierno, V.; Crochet, P.;
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dx.doi.org/10.1021/ic4003687 | Inorg. Chem. 2013, 52, 5428−5437