Cationic Trimers
1544±1564
[2] a) D. F. Dersnah, M. C. Baird, J. Organomet. Chem. 1977, 127, C55;
b) W. S. Sheldrick, S. Heeb, Inorg. Chim. Acta 1990, 168, 93.
[3] The experimental values for the coefficients B in the Onsager
equation Leq L0 Bc1/2 were 348.5 (M Rh, Aa Ala), 622.5
(M Ir, Aa Ala), 347.8 (M Rh, Aa l-Pro), and 627.9 (M Ir,
Aa l-Pro). a) R. D. Feltham, R. G. Hayter, J. Chem Soc. 1964, 4587;
b) W. J. Geary, Coord. Chem. Rev. 1971, 7, 81.
[4] R. Krämer, K. Polborn, C. Robl, W. Beck, Inorg. Chim. Acta 1992,
198 ± 200, 415.
[5] a) Aqueous Organometallic Chemistry and Catalysis. (Eds.: I. T.
[23] The method applied is analogous to that described in: a) D. Braga, F.
Grepioni, P. Sabatino, J. Chem. Soc. Dalton Trans. 1990, 3137; b) D.
Braga, F. Grepioni, Organometallics 1991, 10, 1254.
[24] A. Gavezzotti, OPEC, Organic Packing Potential Energy Calculations.
University of Milano, Italy, 1987. See also: A. Gavezzotti, J. Am.
Chem. Soc. 1983, 95, 5220.
[25] The tetrafluoroborate trimers are almost insoluble in CHCl3, Et2O,
and hydrocarbon solvents. Due to solubility reasons we were not able
to carry out solution measurements for the following solvent/complex
pairs: in dichloromethane, acetone, methanol, and water, compounds
1a, 2a, 9a, and 9b; in dichloromethane, methanol, and water,
compounds 3a and 5a; in dichloromethane, compounds 1c, 3c, 4b,
and 9c; in methanol and water, compound 3b and in water,
compounds 4c and 5b.
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Horvath, F. Joo) NATO ASI Series: High Technology, Vol. 5, Kluwer,
Dordrecht, 1995; b) Aqueous Organometallic Catalysis - Principles
and Applications (Eds.: B. Cornils, W. A. Herrmann), WILEY-VCH,
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Weinheim, 1998; c) Catalysis in Water (Ed.: I. T. Horvath) Special
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issue of J. Mol. Catal. A 1995, 116; d) F. Joo, J. Kovacs, A.Cs. Benyei,
[26] The composition of the mixtures was obtained by careful integration
of the corresponding C5Me5 (rhodium and iridium trimers) or methyl
arene protons (ruthenium derivatives) of each diastereomer. Error
limits in each integral are estimated as Æ2%.
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A. Katho, Angew. Chem. 1998, 110, 1024; Angew. Chem. Int. Ed. 1998,
37, 969.
[6] a) P. A. Chaloner, M. A. Esteruelas, F. Joo, L. A. Oro, Homogeneous
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Hydrogenation (Catalysis by Metal Complexes, Vol 15), Kluwer,
Dordrecht, 1994; b) R. Noyori, S. Hashiguchi, Acc. Chem. Res. 1997,
30, 97; c) T. Langer, G. Helmchen, Tetrahedron Let. 1996, 37, 1381.
[7] a) S. Hashiguchi, A. Fujii, J. Takehara, T. Ikariya, R. Noyori, J. Am.
Chem. Soc. 1995, 117, 7562; b) R. L. Chowdhury, J.-E. Bäckvall, J.
Chem. Soc. Chem. Commun. 1991, 1063; c) P. Kvintovics, B. R. James,
B. Heil, J. Chem. Soc. Chem. Commun. 1986, 1810; d) J.-X. Gao, T.
Ikariya, R. Noyori, Organometallics, 1996, 15, 1087; e) P. Krasik, H.
Alper, Tetrahedron, 1994, 50, 4347.
[27] The CD and some NOEDIFF spectra of the rhodium trimers are
included as supplementary material.
[28] Again, the l-prolinate complexes 6a,b behaved differently, the
amount of the 1 diastereomer increasing with time.
[29] Diastereomeric compositions for the iridium trimers 3b, 4b, 6b, and
8b are included in the supplementary material.
[30] R. G. Wilkins, Kinetics and Mechanism of Reactions of Transition
Metal Complexes (2nd ed), VCH, Weinheim, 1991, p. 13.
[31] Recently, Fish et al. reported that only the s diastereomer of the
phenyl alaninate rhodium trimer [{(h5-C5Me5)Rh(Phe)}3](BF4)3 (5a)
was present in D2O (pD, 6) from 5 to 658C: S. Ogo, H. Chen, M. M.
Olmstead, R. H. Fish, Organometallics 1996, 15, 2009.
[8] a) L. A. Oro, D. Carmona, J. Reedijk, Inorg. Chim. Acta 983, 71, 115;
b) L. A. Oro, D. Carmona, M. P. Lamata, A. Tiripicchio, F. J. Lahoz, J.
Chem. Soc. Dalton Trans. 1986, 15.
[9] C. J. Jones, J. A. McCleverty, A. S. Rothin, J. Chem. Soc. Dalton Trans.
1986, 109.
[32] Surprisingly, the diastereomerisation of the iridium compound 8b in
water was accompanied by partial deuteration of the N ± Me amino
acidate group. We have no satisfactory explanation for this.
[33] D. G. McCollum, C. Fraser, R. Ostrander, A. L. Rheingold, B.
Bosnich, Inorg. Chem. 1994, 33, 2383.
[10] K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordina-
tion Compounds, 4th ed., Wiley-Interscience, New York, 1986, p. 132.
[11] W. S. Sheldrick, R. Exner, Inorg. Chim. Acta 1989, 166, 213.
[12] The sequence rules establish the following priority order: h-ring > O
quelate > O bridging > N. See: a) R. S. Cahn, C. Ingold, V. Prelog,
Angew. Chem. 1966, 78, 413, Angew. Chem. Int. Ed. Engl. 1966, 4, 385;
b) V. Prelog, G. Helmchen, Angew. Chem. 1982, 94, 614, Angew.
Chem. Int. Ed. Engl. 1982, 21, 576; c) C. Lecomte, Y. Dusausoy, J.
Protas, J. Tirouflet, J. Organomet. Chem. 1974, 73, 67; d) K. Stanley,
M. C. Baird, J. Am. Chem. Soc. 1975, 97, 6599; e) T. E. Sloan, Top.
Stereochem. 1981, 12, 1.
[34] Obviously, for the d-prolinate compound 7c the corresponding
enantiomers of the l-prolinate 6c were observed in each case, as
assayed by CD spectroscopy.
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[35] a) H. Shertchook, D. Avnir, J. Blum, F. Joo, A. Katho, H. Schumann,
R. Weimann, S. Wernik, J. Mol. Catal. A, 1996, 108, 153; b) A.
Rosenfeld, D. Avnir, J. Blum, J. Chem. Soc. Chem. Commun. 1993,
583; c) D. Avnir, S. Braun, M. Ottolenghi, Am. Chem. Soc. Symp. Ser.
1992, 499, 384.
[13] A detailed search of 'M(pro)' fragments in the CSD file showed all the
structures to have identical chirality for the a-carbon and for the
coordinated aminic nitrogen of the aminoacidate ligand. See also:
a) R. D. Gillard, O. P. Slyudkin, J. Chem. Soc. Dalton Trans. 1978, 152;
b) H. Kollowski, L. D. Pettit in Chemistry of the Platinum Group
Metals (Ed.: F. R. Hartley), Elsevier, New York, 1991, Ch. 15, p. 530.
[14] R. Atencio, PhD Thesis, University of Zaragoza, 1995, Zaragoza.
[15] The configuration around the metal centre in [{(h5-C5Me5)-
Rh(Phe)}3]3 is identical to that observed in 1b, but the chiral
[36] E. L. Eliel, S. H. Wilen, L. N. Mander, Stereochemistry of Organic
Compounds, Wiley-Interscience, New York, 1994, p. 365.
[37] For recently reported organometallic examples see: a) H. Brunner, R.
Oeschey, B. Nuber, J. Chem. Soc. Dalton Trans. 1996, 1499; b) H.
Brunner, R. Oeschey, B. Nuber, Organometallics 1996, 15, 3616.
[38] T. Ohkuma, H. Ooka, T. Ikariya, R. Noyori, J. Am. Chem. Soc. 1995,
117, 10417.
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[39] a) F. Joo, A. Benyei, J. Organomet. Chem. 1989, 363, C19; b) A.
Â
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Benyei, F. Joo, J. Mol. Catal. 1990, 58, 151; c) D. J. Darensbourg, F. Joo,
descriptors assigned in the original paper[4] are opposite: SRhSRhSRh
.
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M. Kannisto, A. Katho, J. H. Reibenspies, D. J. Daigle, Inorg. Chem.
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[16] I. Zahn, K. Polborn, B. Wagner, W. Beck, Chem. Ber. 1991, 124, 1065.
1994, 33, 200; d) D. J. Darensbourg, F Joo, M. Kannisto, A. Katho,
[17] D. Carmona, F. J. Lahoz, R. Atencio, L. A. Oro, M. P. Lamata, E. San
J. H. Reibenspies, Organometallics 1992, 11, 1992.
Â
Jose, Tetrahedron Asymmetry 1993, 4, 1425.
[40] a) G. Allmang, F. Grass, J. M. Grosselin, C. Mercier, J. Mol. Catal.
1991, 66, L27; b) J. M. Grosselin, C. Mercier, G. Allmang, F. Grass, F.
Organometallics 1991, 10, 2126.
[18] D. B. Grotjahn, C. Joubran, J. L. Hubbard, Organometallics 1996, 15,
1230.
[19] F. H. Allen, J. E. Davies, J. J. Galloy, O. Johnson, O. Kennard, C. F.
Macrae, E. M. Mitchell, G. F. Mitchell, J. M. Smith, D. G. Watson J.
Chem. Inf. Comput. Sci. 1991, 31, 187.
[20] For the d-prolinate compounds 7 the configurations at the carbon and
nitrogen atoms are R. The configuration at the HC(OH) carbon of the
4-OH-l-prolinate complexes 9 is R and it is not quoted in the general
descriptors.
[21] The term trimer molecule in this analysis refers to a set of atoms that
include all the crystallographically independent atoms of the trinu-
clear complex and those of only one of the two disordered BF4 groups
(B(3), F(1c) ± F(4c)).
[22] a) A. J. Pertsin, A. Kitaigorodski, The Atom-Atom Potential Method,
Springer, Berlin, 1987; b) A. Gavezzotti, M. Simonetta, Organic Solid
State Chemistry (Ed.: G. R. Desiraju), Elsevier, Amsterdam, 1987.
[41] a) G. Zassinovich, G. Mestroni, S. Gladiali, Chem. Rev. 1992, 92, 1051;
b) G.-Z. Wang, J.-E. Bäckvall, J. Chem. Soc. Chem. Commun. 1992,
980; c) Z. Yuskovetz, M. Shimanska, Khim. Geterocikl. Soed. 1994,
435; d) M. Palmer, T. Walsgrove, M. Wills, J. Org. Chem. 1997, 62,
5226; e) D. A. Alonso, D. Guijarro, P. Pinho, O. Temme, P. G.
Andersson, J. Org. Chem. 1998, 63, 2749; f) L. Schwink, T. Ireland, K.
Püntener, P. Knochel, Tetrahedron: Asymmetry. 1998, 9, 1143; g) C.
Bianchini, L. Glendenning, F. Zanobini, E. Farnetti, M. Graziani, E.
Nagy, J. Mol. Catal. A. 1998, 132, 13.
[42] E. Mizushima, M. Yamaguchi, T.Yamagishi, Chem. Let. 1997, 237.
[43] T. Ohkuma, H. Ooka, S. Hashiguchi, T. Ikariya, R. Noyori, J. Am.
Chem. Soc. 1995, 117, 2675.
[44] H. Yang, M. Alvarez, N. Lugan, R. Mathieu, J. Chem. Soc. Chem.
Commun. 1995, 1721.
Chem. Eur. J. 1999, 5, No. 5
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