Isolation and characterization of unusual multinuclear ... · S2 Copies of NMR and MS spectra for...

Electronic Supporting Information (ESI) for:

Isolation and characterization of unusual multinuclear Schiff

base complexes: Rearrangements reactions and octanuclear

cluster formation

Marta Martínez Belmonte,a Eduardo C. Escudero-Adán,

a Eddy Martin,

and Arjan W. Kleij*a,b

aInstitute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans

16, 43007, Tarragona, Spain. E-mail: akleij@iciq.es; Fax: +34 977920224; Tel: +34

977920247

bCatalan Institute for Research and Advanced Studies (ICREA), Pg. Llu´ıs

Companys 23, 08010, Barcelona, Spain

Contents:

Page S2: Copies of NMR and MS spectra for compounds 1-11.

Page S33: NMR conversion of 1 into 4 in DMSO-d6 at 130ºC.

Page S34: Comparison of 1H NMR traces for the conversion of 12.

Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2012

Copies of NMR and MS spectra for compounds 1-11:1

1H NMR spectrum (DMSO-d6) for 1:

*Please note the peak located around = 1.8 ppm indicating the presence of OAc.

1 Please note that in the case of the

1H NMR experiments DEPT was used. In some cases, the

NMR traces are of mediocre quality as a result of the rather low solubility of the respective complexes.

1H NMR spectrum (pyridine-d5) for 1:

MALDI(+) MS (dctb) for 1:

Calculated pattern for Zn8 complex 1 (C38H40N4O12Zn4·dctb·Na):

Note the data for dctb below:

Enlargement of the area 5.5 – 10 ppm:

Calculated pattern for Zn8 complex 2 (C82H62N6O16Zn8):

MS analysis of 5:

Note that complex 3 was not very soluble under the MS conditions used.

MS analysis of 4:

Calculated pattern for Zn8 complex 4 (C42H36N4O12Zn4·dctb·Zn):

Note the data for dctb below:

1H NMR spectrum (Acetone-d6) for 5:

MALDI(+) MS (dctb) for 6 (enlargement):

1H NMR spectrum (DMSO-d6) for 8, enlargement of aromatic region:

MALDI(+) MS (dctb) for 8 (enlargement):

X-ray diffraction analysis for 8:

Displacement ellipsoids shown at the 50% probability level; note that the co-crystallized

solvent molecules and H-atoms are omitted for clarity. Only a partial numbering scheme

(for the Zn centres) is provided here.

1H NMR (EXTENDED region) spectrum (DMSO-d6) for 9:

POV-RAY presentation of the X-ray structure determined for 10:

Note the presence of four 3,5-dimethylpyridines coordinating to some of the Zn centres

that are highlighted in green. Co-crystallized solvent molecules and H-atoms are

omitted for clarity.

1H NMR (DMSO-d6) of the crystalline material obtained for the conversion of 110:

Comparison between pure complex 6 and the crystalline material (10) obtained after

treatment of 1 with pyridine:

On top in RED: aromatic region for the pure complex 6.

Below, in BLACK the same aromatic region for the crystalline material of the

conversion 110.

MALDI(+) MS (dctb) for 10, showing the cluster around m/z = 1445:

Please note the resemblance with the isotopic cluster for complex 6.

X-ray structure (ORTEP) determined for 11:

1H NMR (DMSO-d6) of the crystalline material obtained for the conversion of 411:

Comparison between pure complex 8 and the crystalline material (11) obtained after

treatment of 4 with pyridine:

On top in RED: aromatic region for the pure complex 8.

Below, in BLACK the same aromatic region for the crystalline material of the

conversion 411.

Please note the resemblance with the isotopic cluster for complex 8.

NMR conversion of 1 into 6 in DMSO-d6 at 130ºC.

Pure (1)

Pure (6)

(1) + aldehyde @ r.t.; 6 h

(1) + aldehyde @ 130ºC; 3 h

(1) + aldehyde @ 130ºC; 16 h

The salicylaldehyde used was 2,3-dihydroxy-benzaldehyde; the reaction was carried out

in an NMR tube using DMSO-d6 as solvent. Amounts: 1 (7.5 mg, 0.00746 mmol), 2,3-

dihydroxy-benzaldehyde (2.0 mg, 0.0145 mmol) and DMSO-d6 (0.5 mL).

Comparison of 1H NMR traces for the conversion of 12.

Note that this experiment was repeated twice with virtually the same result. Below only

the aromatic region is shown (DMSO-d6):

On top, in RED, the pure crystalline complex 2 in DMSO-d6.

Below in BLACK the complex isolated after treatment of 1 with 2,3-

dihydroxybenzaldehyde in pyridine. Some residual pyridine (reaction solvent) is also

present.

On top, in RED, the pure complex 7 in DMSO-d6.2

dihydroxybenzaldehyde in pyridine.

2 For the synthesis and further analysis of this complex refer to: R. M. Haak, A. Decortes, E. C. Escudero-

Adán, M. Martínez Belmonte, E. Martin, J. Benet-Buchholz and A. W. Kleij, Inorg. Chem., 2011, 50,

On top, in RED, the independently prepared complex 8 in DMSO-d6.

dihydroxybenzaldehyde in pyridine. Traces of residual pyridine (reaction medium) are

also present.

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