10.1002/ejic.201700727
European Journal of Inorganic Chemistry
FULL PAPER
Goodness of fit on F2
R [F2 2(F2)][a]
1.053
Carrillo-Hermosilla, Organometallics 2015, 34, 2796-2809; c) J.
Francos, P. J. González-Liste, L. Menéndez-Rodríguez, P. Crochet, V.
Cadierno, J. Borge, A. Antiñolo, R. Fernández-Galán, F. Carrillo-
Hermosilla, Eur. J. Inorg. Chem. 2016, 393-402.
0.0293
wR(F2) [F2 2(F2)][a]
0.0712
R (all data)
wR(F2) (all data)
Largest diff peak and hole [e·Å-3]
0.0342
[4]
[5]
R. Kishan, R. Kumar, S. Baskaran, C. Sivasankar, N. Thirupathi, Eur. J.
Inorg. Chem. 2015, 3182-3194.
0.0749
0.568 and -0.649
½
For specific review articles covering the chemistry of bicyclic
guanidinate ligands, see: a) M. P. Coles, Chem. Commun. 2009, 3659-
3676; b) C. A. Murillo, Aust. J. Chem. 2014, 67, 972-979.
[a] R = Fo - Fc/Fo; wR(F2) = {[w(Fo2 - Fc2)2]/[w(Fo2)2]} .
[6]
For reviews on the redox isomerization of allylic alcohols, see: a) R.
Uma, C. Crévisy, R. Grée, Chem. Rev. 2003, 103, 27-51; b) R. C. van
der Drift, E. Bouwman, E. Drent, J. Organomet. Chem. 2002, 650, 1-24;
c) V. Cadierno, P. Crochet, J. Gimeno, Synlett 2008, 1105-1124; d) P.
Lorenzo-Luis, A. Romerosa, M. Serrano-Ruiz, ACS Catal. 2012, 2,
1079-1086; e) J. García-Álvarez, S. E. García-Garrido, P. Crochet, V.
Cadierno, Curr. Top. Catal. 2012, 10, 35-56.
Acknowledgements
This work was supported by the Ministerio de Economía y
Competitividad (MINECO) of Spain (projects CTQ2013-40591-P
and CTQ2016-75986-P) and the Gobierno del Principado de
Asturias (project GRUPIN14-006). J.F. thanks MINECO and the
European Social Fund (ESF) for the award of a “Juan de la
Cierva” contract (IJCI-2014-19174). Prakash Chemicals
(Budaun, India) is also acknowledged for the generous gift of the
estragole employed in this work.
[7]
[8]
For a review covering the catalytic isomerization of allyl-benzenes, see:
M. Hassam, A. Taher, G. E. Arnott, I. R. Green, W. A. L. van Otterlo,
Chem. Rev. 2015, 115, 5462-5569.
The guanidinium salts 3a-c are known compounds. See, for example:
a) B. Linton, A. D. Hamilton, Tetrahedron 1999, 55, 6027-6038; b) M. S.
Khalaf, S. H. Oakley, M. P. Coles, P. B. Hitchcock, CrystEngComm
2008, 10, 1653-1661; c) Z.-Z. Yang, L.-N. He, C.-X. Miao, S. Chanfreau,
Adv. Synth. Catal. 2010, 352, 2233-2240; d) S. Foltran, J. Alsarraf, F.
Robert, Y. Landais, E. Cloutet, H. Cramail, T. Tassaing, Catal. Sci.
Technol. 2013, 3, 1046-1055.
Keywords: Ruthenium • Osmium • Guanidinate ligands •
Homogeneous catalysis • Allylic Alcohols • Anethole
[9]
By analogy with the case of the cyclohexane molecule, Cotton, Murillo
and co-workers also proposed that the “twist-chair” and “chair”
conformers should be thermodynamically more stable that “boat” one.
See reference [2i].
[1]
For review articles covering the chemistry of metal-guanidinate
complexes, see: a) P. J. Bailey, S. Pace, Coord. Chem. Rev. 2001, 214,
91-141; b) W. E. Piers, D. J. H. Emslie, Coord. Chem. Rev. 2002, 233-
234, 131-155; c) F. T. Edelmann, Adv. Organomet. Chem. 2008, 57,
183-352; d) F. T. Edelmann, Chem. Soc. Rev. 2009, 38, 2253-2268; e)
C. Jones, Coord. Chem. Rev. 2010, 254, 1273-1289; f) A. A. Trifonov,
Coord. Chem. Rev. 2010, 254, 1327-1347; g) S. Collins, Coord. Chem.
Rev. 2011, 255, 118-138; h) F. T. Edelmann, Chem. Soc. Rev. 2012,
41, 7657-7672; i) F. T. Edelmann, Adv. Organomet. Chem. 2013, 61,
55-374; j) S. T. Barry, Coord. Chem. Rev. 2013, 257, 3192-3201; k) A.
Kurec, P. G. Gordon, S. Karle, A. Devi, S. T. Barry, Aust. J. Chem.
2014, 67, 989-996; l) T. Chlupatý, A. Růžička, Coord. Chem. Rev. 2016,
314, 103-113.
[10] a) Although the coordination of the guanidinate anion hpp to the
[RuCl(6-C6H6)] fragment was evidenced by 1H NMR spectroscopy, the
very low solubility of both [{RuCl(-Cl)(6-C6H6)}2] (4) and [RuCl{2-
(N,N´)-hpp}(6-C6H6)] (6) in conventional organic solvents made
impossible the purification of the crude reaction mixture; b) As an
alternative, the reactivity of 4 towards the sodium salt Nahpp was also
explored, but irrespective of the solvent employed the reactions led to
the formation of a complex mixture of products. Similar observations
were also made starting from dimers 1a-c.
[11] For reviews covering the chemistry of this dimer, see: a) V. Cadierno, P.
Crochet, S. E. García-Garrido, J. Gimeno, Curr. Org. Chem. 2006, 10,
165-183; b) J. Francos, S. E. García-Garrido, J. García-Álvarez, P.
Crochet, J. Gimeno, V. Cadierno, Inorg. Chim. Acta 2017, 455, 398-414.
[12] In reference [3c], under identical reaction conditions, the maximum
conversion of 1-octen-3-ol that could be achieved was 56% after 24 h
employing complex [OsCl{2-(N,N´)-C(N-4-C6H4tBu)(NiPr)-NHiPr}(6-p-
cymene)] as catalyst. At this point we would like to indicate that the
involvement of osmium catalysts in the base-free redox isomerization of
allylic alcohols is scarcely documented: M. Batuecas, M. A. Esteruelas,
C. García-Yebra, E. Oñate, Organometallics 2010, 29, 2166-2175.
[13] This greater stability in water is not an exclusive property of the
bis(allyl)-ruthenium(IV) compound 9, the rest of complexes synthesized
in this work are also stable and catalytically active in this medium. As a
representative example, employing a 0.50 M solution of 1-octen-3-ol in
water and 0.20 mol% of 2a, octan-3-one was generated in quantitative
yield after 3 hours of heating at 80 ºC. Although we have not a definitive
explanation to account for these differences, they may be related to the
higher rigidity and lower steric requirements of hpp in comparison to the
acyclic guanidinates employed previously. Since the decomposition
involves the decoordination of the guanidinate, we assume that the first
step could be a change in its coordination [from 2-(N,N´) to 1-(N)], a
process disfavored in the case of the rigid and less bulky hpp
guanidinate.
[2]
a) P. J. Bailey, L. A. Mitchell, S. Parsons, J. Chem. Soc., Dalton Trans.
1996, 2839-2841; b) J. L. Bear, Y. Li, B. Han, K. M. Kadish, Inorg.
Chem. 1996, 35, 1395-1398; c) M. B. Dinger, W. Henderson, B. K.
Nicholson, J. Organomet. Chem. 1998, 556, 75-88; d) K. T. Holman, S.
D. Robinson, A. Sahajpal, J. W. Steed, J. Chem. Soc., Dalton Trans.
1999, 15-18; e) P. J. Bailey, K. J. Grant, L. A. Mitchell, S. Pace, A.
Parkin, S. Parsons, J. Chem. Soc., Dalton Trans. 2000, 1887-1891; f) S.
D. Robinson, A. Sahajpal, J. Steed, Inorg. Chim. Acta 2000, 303, 265-
270; g) R. Clérac, F. A. Cotton, L. M. Daniels, J. P. Donahue, C. A.
Murillo, D. J. Timmons, Inorg. Chem. 2000, 39, 2581-2584; h) F. A.
Cotton, N. S. Dalal, P. Huang, C. A. Murillo, A. C. Stowe, X. Wang,
Inorg. Chem. 2003, 42, 670-672; i) F. A. Cotton, C. A. Murillo, X. Wang,
C. C. Wilkinson, Inorg. Chim. Acta 2003, 351, 191-200; j) F. A. Cotton,
C. A. Murillo, J. H. Reibenspies, D. Villagrán, X. Wang, C. C. Wilkinson,
Inorg. Chem. 2004, 43, 8373-8378; k) J. S. Pap, J. L. Snyder, P. M. B.
Piccoli, J. F. Berry, Inorg. Chem. 2009, 48, 9846-9852; l) G. M.
Chiarella, F. A. Cotton, C. A. Murillo, M. D. Young, Q. Zhao, Inorg.
Chem. 2010, 49, 3051-3056; m) R. Lee, Y. Yang, G. K. Tan, C.-H. Tan,
K.-W. Huang, Dalton Trans. 2010, 39, 723-725; n) F. A. Cotton, G. M.
Chiarella, N. S. Dalal, C. A. Murillo, Z. Wang, M. D. Young, Inorg.
Chem. 2010, 49, 319-324; o) T. Singh, R. Kishan, M. Nethaji, N.
Thirupathi, Inorg. Chem. 2012, 51, 157-169; p) R. Kishan, R. Kumar, S.
Baskaran, C. Sivasankar, N. Thirupathi, Eur. J. Inorg. Chem. 2015,
3182-3194; q) G. M. Chiarella, C. A. Murillo, M. D. Young, Polyhedron
2015, 103, 15-20.
[14] See, for example: a) P. Crochet, M. A. Fernández-Zúmel, J. Gimeno, M.
Scheele, Organometallics 2006, 25, 4846-4849; b) P, Crochet, J. Díez,
M. A. Fernández-Zumel, J. Gimeno, Adv. Synth. Catal. 2006, 348, 93-
100; c) L. Menéndez-Rodríguez, P. Crochet, V. Cadierno, J. Mol. Catal.
A: Chem. 2013, 366, 390-399.
[3]
a) R. García-Álvarez, F. J. Suárez, J. Díez, P. Crochet, V. Cadierno, A.
Antiñolo, R. Fernández-Galán, F. Carrillo-Hermosilla, Organometallics
2012, 31, 8301-8311; b) L. Menéndez-Rodríguez, E. Tomás-Mendivil, J.
Francos, P. Crochet, V. Cadierno, A. Antiñolo, R. Fernández-Galán, F.
This article is protected by copyright. All rights reserved.