Dalton Transactions
Paper
8 (a) S. B. Wendicke, E. Burri, R. Scopelliti and K. Severin,
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353, 2915.
ably upon addition of a chloride anion source (e.g. NaCl) to
the medium.
9 See, for example: (a) B. Therrien and T. R. Ward, Angew. 15 See, for example: (a) K. Umezawa-Vizzini and T. R. Lee,
Chem., Int. Ed., 1999, 38, 405; (b) Y. Miyaki, T. Onishi and
H. Kurosawa, Inorg. Chim. Acta, 2000, 300–302, 369;
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R. Kunz, C. Bruneau, D. Touchard and P. H. Dixneuf, 16 See, for example: B. Demerseman, R. Le Lagadec,
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D. G. D’Alliessi, Organometallics, 2003, 22, 2749;
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(e) V. Cadierno, J. Díez, J. García-Álvarez and J. Gimeno, 17 The reaction of the precursor [RuCl2(η6-C6H5OCH2CH2OH)-
Chem. Commun., 2004, 1820; (f) J. Čubrilo, I. Hartenbach,
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Catal. Sci. Technol., 2012, 2, 406.
{P(OEt)3}] (1b), under the same experimental conditions
(i.e. r.t., CH2Cl2, 1 equiv. of AgSbF6 per Ru), seems to gener-
ate predominantly the derivative [{Ru(μ-Cl)(η6-C6H5OCH2-
CH2OH){P(OEt)3}}2][SbF6]2 analogous to compound
2
[SbF6]2. However, the presence of inseparable impurities
did not allow the isolation of a pure sample of this deriva-
tive. Structure assignation is based on the similarity of
NMR data with those of compound 2[SbF6]. Spectroscopic
data: 31P{1H} NMR, acetone-d6, δ: 116.6 (s). 1H NMR,
acetone-d6, δ: 6.52 and 6.33 (both m, 2 H each, CHmeta),
10 See, for example: (a) G. Marconi, H. Baier,
F. W. Heinemann, P. Pinto, H. Pritzkow and U. Zenneck,
Inorg. Chim. Acta, 2003, 352, 188; (b) J. Hannedouche,
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B. A. Hess, A. Marinetti, F. W. Heinemann and U. Zenneck,
Organometallics, 2006, 25, 2607; (e) R. Aznar, G. Muller,
3
3
5.60 (d, 2 H, JHH = 6.4, CHortho), 5.06 (d, 2 H, JHH = 6.6,
3
3
CHortho), 4.35 (apparent t, 2 H, JHH ≈ JHH ≈ 5.8, CHpara),
4.09 (m, 12 H, POCH2), 3.89 and 3.79 (both m, 4 H each,
3
CH2CH2), 1.32 (t, 18 H, JHH = 6.9, POCH2Me); OH signal
was not observed.
D. Sainz, M. Font-Bardia and X. Solans, Organometallics, 18 On the other hand, all our attempts to generate [{RuCl-
2008, 27, 1967.
(η6-C6H5OCH2CH2OH){P(OPh)3}}2(μ-Cl)][SbF6], structurally
related to 3[SbF6], from 1a failed. The use of only half an
equivalent of AgSbF6 per Ru gave rise to a mixture of 2
[SbF6]2 and the starting material 1a.
11 A. M. Pizarro, M. Melchart, A. Habtemariam, L. Salassa,
F. P. A. Fabbiani, S. Parsons and P. J. Sadler, Inorg. Chem.,
2010, 49, 3310.
12 B. Lastra-Barreira and P. Crochet, Green Chem., 2010, 12, 19 A mixture of [{Ru(η6-C6Me6)}2(μ-Cl)3][PF6] and [Ru-
1311.
(η6-C6Me6)(η6-C6H5PPh2)][PF6] was rather obtained. See:
H. Werner, H. Kletzin and C. Burschka, J. Organomet.
Chem., 1984, 276, 231.
13 (a) V. Cadierno, P. Crochet, S. E. García-Garrido and
J. Gimeno, Dalton Trans., 2004, 3635; (b) P. Crochet,
J. Díez, M. A. Fernández-Zúmel and J. Gimeno, Adv. Synth. 20 Y. Miyaki, T. Onishi, S. Ogoshi and H. Kurosawa, J. Organo-
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Zúmel, J. Gimeno and M. Scheele, Organometallics, 2006, 21 Complex 5c was previously obtained as the corresponding
25, 4846; (d) A. E. Díaz-Álvarez, P. Crochet, M. Zablocka, tetrafluoroborate salt. See ref. 9b.
C. Duhayon, V. Cadierno, J. Gimeno and J. P. Majoral, Adv. 22 This difference in reactivity is also exemplified by their
Synth. Catal., 2006, 348, 1671; (e) V. Cadierno, J. Francos,
J. Gimeno and N. Nebra, Chem. Commun., 2007, 2536;
(f) V. Cadierno, P. Crochet and J. Gimeno, Synlett, 2008,
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M. Scheele, J. Díez, P. Crochet and J. Gimeno, Dalton
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V. Cadierno, Catal. Commun., 2011, 13, 91; ( j) J. García-
Álvarez, S. E. García-Garrido, P. Crochet and V. Cadierno,
Curr. Top. Catal., 2012, 10, 35; (k) R. García-Álvarez,
F. J. Suárez, J. Díez, P. Crochet, V. Cadierno, A. Antiñolo,
behavior in the aqueous medium. The dissolution of
[RuCl2(η6-C6H5OCH2CH2OH){P(OEt)3}] (1b) in D2O gave
rise to a mixture of [RuCl(D2O)(η6-C6H5OCH2CH2OH)-
{P(OEt)3}][Cl] and the starting product 1b, due to partial
dissociation of one chloride ligand. In contrast, aqueous
solutions of the analog 4b contain three species: (i) the
starting material 4b, (ii) the aquo-complex [RuCl(D2O)(η6-
C6H5CH2CH2CH2OH){P(OEt)3}][Cl], generated by displace-
ment of a Cl ligand by a molecule of water and, (iii) the
tethered derivative [RuCl(η6:κ1(O)-C6H5CH2CH2CH2OH)-
{P(OEt)3}][Cl], formed through Cl− release and coordi-
nation of the hydroxyl group of the arene side chain onto
the metal center (see NMR data in the ESI†).
R.
Fernández-Galán
and
F.
Carrillo-Hermosilla,
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Dalton Trans., 2013, 42, 5412–5420 | 5419