isolation and characterization of unusual multinuclear ... · s2 copies of nmr and ms spectra for...
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![Page 1: Isolation and characterization of unusual multinuclear ... · S2 Copies of NMR and MS spectra for compounds 1-11:1 1H NMR spectrum (DMSO-d 6) for 1: *Please note the peak located](https://reader034.vdocuments.us/reader034/viewer/2022042413/5f2d53eca8a6e10b782099f3/html5/thumbnails/1.jpg)
S1
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,
a
and Arjan W. Kleij*a,b
aInstitute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans
16, 43007, Tarragona, Spain. E-mail: [email protected]; 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.
Page S35: Comparison of 1H NMR traces for the conversion of 37.
Page S36: Comparison of 1H NMR traces for the conversion of 48.
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S2
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
13C
1H NMR experiments DEPT was used. In some cases, the
13C
NMR traces are of mediocre quality as a result of the rather low solubility of the respective complexes.
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S3
13C
1H NMR spectrum (pyridine-d5) for 1:
MALDI(+) MS (dctb) for 1:
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S4
Calculated pattern for Zn8 complex 1 (C38H40N4O12Zn4·dctb·Na):
Note the data for dctb below:
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S5
1H NMR spectrum (DMSO-d6) for 2:
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S6
Enlargement of the area 5.5 – 10 ppm:
MALDI(+) MS (dctb) for 2:
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S7
Calculated pattern for Zn8 complex 2 (C82H62N6O16Zn8):
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S8
1H NMR spectrum (DMSO-d6) for 3:
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S9
13C
1H NMR spectrum (DMSO-d6) for 3:
MS analysis of 5:
Note that complex 3 was not very soluble under the MS conditions used.
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S10
Calculated pattern for Zn8 complex 3 (C34H32N4O12Zn4):
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S11
1H NMR spectrum (DMSO-d6) for 4:
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S12
MS analysis of 4:
Calculated pattern for Zn8 complex 4 (C42H36N4O12Zn4·dctb·Zn):
Note the data for dctb below:
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S13
1H NMR spectrum (Acetone-d6) for 5:
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S14
13C
1H NMR spectrum (Acetone-d6) for 5:
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S15
1H NMR spectrum (DMSO-d6) for 6:
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S16
13C
1H NMR spectrum (DMSO-d6) for 6:
MALDI(+) MS (dctb) for 6:
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S17
MALDI(+) MS (dctb) for 6 (enlargement):
Calculated pattern for Zn8 complex 6 (C88H64N8O16Zn8):
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S18
1H NMR spectrum (DMSO-d6) for 8:
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S19
1H NMR spectrum (DMSO-d6) for 8, enlargement of aromatic region:
MALDI(+) MS (dctb) for 8:
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S20
MALDI(+) MS (dctb) for 8 (enlargement):
Calculated pattern for Zn8 complex 8 (C88H64N8O16Zn8):
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S21
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.
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S22
1H NMR spectrum (DMSO-d6) for 9:
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S23
1H NMR (EXTENDED region) spectrum (DMSO-d6) for 9:
13C
1H NMR spectrum (DMSO-d6) for 9:
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S24
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.
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S25
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.
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S26
MALDI(+) MS (dctb) for 10:
MALDI(+) MS (dctb) for 10, showing the cluster around m/z = 1445:
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S27
MALDI(+) MS (dctb) for 10, showing the cluster around m/z = 2011:
Please note the resemblance with the isotopic cluster for complex 6.
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S28
X-ray structure (ORTEP) determined for 11:
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S29
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.
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S30
MALDI(+) MS (dctb) for 11:
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S31
MALDI(+) MS (dctb) for 11, showing the cluster around m/z = 1512:
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S32
MALDI(+) MS (dctb) for 11, showing the cluster around m/z = 2100:
Please note the resemblance with the isotopic cluster for complex 8.
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S33
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).
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S34
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.
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S35
Comparison of 1H NMR traces for the conversion of 37.
On top, in RED, the pure complex 7 in DMSO-d6.2
Below in BLACK the complex isolated after treatment of 3 with 2,3-
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,
7934.
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S36
Comparison of 1H NMR traces for the conversion of 48.
On top, in RED, the independently prepared complex 8 in DMSO-d6.
Below in BLACK the complex isolated after treatment of 4 with 2,3-
dihydroxybenzaldehyde in pyridine. Traces of residual pyridine (reaction medium) are
also present.
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