173.8 (CO). IR (KBr, cmϪ1); ν(NH) 3416s, ν(NH2) 3323s and
3200m, ν(amide I) 1680s, ν(amide II) 1635s. Mp 149 ЊC. Mass
spectrometry (EI): m/z 165.1.
5 R. A. Johnson, K. B. Sharpless and E. N. Jacobsen, in Catalytic
Asymmetric Synthesis, ed. I. Ojima, VCH, New York, 1993, ch. 4;
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McAuliffe, R. G. Pritchard, M. Watkinson and V. Lukov, Inorg.
Chim. Acta, 1999, 293, 210; (d) M. Maneiro, M. R. Bermejo,
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McAuliffe, Polyhedron, 2000, 19, 47.
7 T. J. Collins and S. W. Gordon-Wylie, J. Am. Chem. Soc., 1989, 111,
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9 P.-H. Ko, T.-Y. Chen, J. Zhu, K.-F. Cheng, S.-M. Peng and C.-M.
Che, J. Chem. Soc., Dalton Trans., 1995, 2215.
10 (a) M. R. Bermejo, A. M. González, M. Fondo, A. García-Deibe,
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Chem., 2000, 24, 235; (b) M. R. Bermejo, A. M. González,
M. Fondo, M. Maneiro, M. Rey, M. Vázquez, O. L. Hoyos and
J. C. García-Monteagudo, Inorg. Chim. Acta, in press; (c) A. M.
González, Ph.D. Thesis, Universidad de Santiago de Compostela,
1999.
11 M. J. Hannon, C. L. Painting, A. Jackson, J. Hamblin and W.
Errington, Chem. Commun., 1997, 1807; M. J. Hannon, S. Bunce,
A. J. Clarke and N. W. Alcock, Angew. Chem., Int. Ed., 1999, 38,
1277 and references therein; R. Ziessel, L. Douce, A. El-ghayoury,
A. Harriman and A. Skoulius, Angew. Chem., Int. Ed., 2000, 39,
1489 and references therein.
12 L. J. Boucher and C. G. Coe, Inorg. Chem., 1975, 14, 1289.
13 J. C. Sheenan and G. P. Hess, J. Am. Chem. Soc., 1955, 77, 1067.
14 A. E. Jackson and R. A. W. Johnstone, Synthesis, 1976, 685.
15 M. R. Bermejo, A. Castiñeiras, J. C. García-Monteagudo, M. Rey,
A. Sousa, M. Watkinson, C. A. McAuliffe, R. G. Pritchard and
R. L. Beddoes, J. Chem. Soc., Dalton Trans., 1996, 2935.
16 W. I. Geary, Coord. Chem. Rev., 1971, 7, 81.
17 C. Piguet, G. Bernardinelli and G. Hopfgartner, Chem. Rev., 1997,
97, 2006; C. Piguet and J.-C. G. Bünzli, Chem. Soc. Rev., 1999, 28,
347; F. Renaud, C. Piguet, G. Bernardinelli, J.-C. G. Bünzli and
G. Hopfgartner, J. Am. Chem. Soc., 1999, 121, 9326.
Preparation of Schiff base ligands. The Schiff base ligands
were prepared in a standard manner by the reaction of equi-
molecular quantities of the appropriate aldehyde and amine 2
which is typified by the preparation of H3phenglydisal-3-Br,5-
Cl. Amine 2 (0.76 g, 4.6 mmol) and 3-bromo-5-chlorosalicyl-
aldehyde (2.18 g, 9.2 mmol) were dissolved in methanol (100
cm3) and the solution was brought to reflux. The volume of the
resulting solution was reduced over 3 h to ca. 50 cm3, using a
Dean–Stark trap and the solution was then allowed to cool. The
solid which precipitated was collected by filtration, washed
with diethyl ether (3 cm3) and dried in vacuo. The purity of the
prepared ligands was checked by elemental analysis, mass
1
spectrometry (Table 1), IR (Table 2) and H NMR spectro-
scopy (Table 3). The 13C NMR spectra of all the ligands in
dmso-d6 show 17 signals corresponding the aromatic, imine and
carbonyl carbon atoms, which lie in the range δ 108.1–168.2.
Additionally, the methylene carbon of the chain and the
methoxy and ethoxy substituents, when present, give separate
signals below δ 70.
Synthesis of the complexes
The synthesis is typified by the preparation of [Mn(phengly-
disal-3-Br,5-Cl)(H2O)]: To a suspension of H3-phenglydisal-3-
Br,5-Cl (0.50 g, 0.83 mmol) in methanol–ethanol (1:1, 80 cm3),
manganese() perchlorate hexahydrate (0.33 g, 0.91 mmol) dis-
solved in methanol (10 cm3) was added and the mixture stirred
for 12 h. Then an aqueous solution of 10 M NaOH (1 cm3) was
added and a rapid change of the solution colour intensity was
observed (CAUTION: all perchlorates are potentially explosive.
Although no problems have been encountered during this
study, care should be taken in the handling and treatment of
these materials). After stirring in the presence of air for three
days, the solid formed was collected by filtration, washed with
water and diethyl ether and dried in vacuo. The complexes were
obtained in high yield and with high purity.
Crystallographic measurements
18 D. E. Fenton, R. W. Mattews, M. McPartlin, B. P. Murphy,
I. J. Scowen and P. A. Tasker, J. Chem. Soc., Chem. Commun., 1994,
1391; R. W. Matthews, M. McPartlin and I. J. Scowen, J. Chem.
Soc., Dalton Trans., 1997, 2861.
19 S. C. Shoner, A. M. Nienstedt, J. J. Ellison, I. Y. Kung, D. Barnhart
and J. A. Kovacs, Inorg. Chem., 1998, 37, 5721.
20 M. R. Bermejo, A. García-Deibe, J. Sanmartín, A. Sousa,
N. Aurangzeb, C. E. Hulme, C. A. McAuliffe, R. G. Pritchard and
M. Watkinson, J. Chem. Soc., Chem. Commun., 1994, 645.
21 E. Iengo, G. Mestroni, S. Geremia, M. Calligaris and E. Alessio,
J. Chem. Soc., Dalton Trans., 1999, 3361.
22 L. J. Bellamy, The infrared spectra of complex molecules, 2nd edn.,
Chapman and Hall, London, 1980; K. Nakamoto, Infrared and
Raman Spectra of Inorganic and Coordination Compounds, 5th edn.,
John Wiley & Sons, New York, 1997.
Crystal data and refinement details are given in Table 5.
Crystals of 3 suitable for single X-ray diffraction studies were
obtained as previously described. Data were collected at 293 K
using a Nicolet P3 diffractometer employing graphite-mono-
chromated Mo-Kα (λ = 0.71073 Å) radiation, using θ–2θ scans.
The structure was solved by direct methods27,28 and refined
by full-matrix least squares on F 2. An analytical absorption
correction was applied. All hydrogen atoms were included in
calculated positions.
CCDC reference number 186/2124.
Acknowledgements
23 J. A. Bonadies, M. J. Maroney and V. L. Pecoraro, Inorg. Chem.,
1989, 28, 2044.
24 A. García-Deibe, M. R. Bermejo, A. Sousa, C. A. McAuliffe,
P. McGlynn, P. T. Ndifon and R. G. Pritchard, J. Chem. Soc., Dalton
Trans., 1993, 1605; M. R. Bermejo, M. Fondo, A. García-Deibe,
M. Rey, J. Sanmartín, A. Sousa and M. Watkinson, Polyhedron,
1996, 15, 4185.
25 E. J. Larson and V. L. Pecoraro, J. Am. Chem. Soc., 1991, 113,
3810.
26 M. Koikawa, H. Ôkawa and S. Kida, J. Chem. Soc., Dalton Trans.,
1988, 641.
We thank Xunta de Galica (20903B) and Ministerio de
Educación y Ciencia (PB98-0600) for financial support. One
of us (O. L. H.) also thanks Instituto de Cooperación
Iberoamericana for a grant.
References
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3127