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Dalton Transactions
Page 6 of 7
DOI: 10.1039/C8DT01170B
ARTICLE
Journal Name
A sample of Hsma (0.0565 g, 0.2974 mmol) was dissolved in 2
mL of ethanol. Ni(C2H3O2)2• 4 H2O (0.0367 g, 0.1477 mmol) was
dissolved in 3 mL of DI water and stirred under nitrogen. The
selenomaltol mixture was added drop wise to the nickel solution,
forming a dark purple precipitate. An additional 10 ml of water was
added to further facilitate precipitation. The resulting mixture was
filtered and washed with 5ml of hexanes twice and an additional 5
ml of DI water. The solid was placed under vacuum to dry overnight
and yielded 0.0486 g (79%) of a black solid. The compound was
crystallized in CH2Cl2 by vapor diffusion with diethyl ether to
produce samples suitable for X-ray diffraction. 1H NMR (600 MHz,
CDCl3): δ 7.50 (d,1H), 7.42 (d,1H), 2.45 (s, 3H). 13C NMR (600 MHz,
CDCl3): δ 175, 167, 154, 142, 124, 16. ESI-MS: m/z (pos.) 436.8341
(M+H).
All calculaꢀons were done at the B3LYP/6-311+G(d,p)
computaꢀonal level using Gaussian09.31 For the NICS
calculaꢀons, the GIAO method was used to calculate the
magneꢀc shielding tensor of a ghost atom. Due to the systems
being symmetrical, the NICS values for only one of the rings are
shown. Firstly, the ring is aligned along the x and y-axes so the
face of the ring is in the z-direcꢀon. Next, a ghost atom is
placed in the center of the ring either within the same plane
(NICS(0)iso) or 1.0 Å above the ring (NICS(1)zz). A property of
ghost atoms is that they will not interact with other atoms, so
the NICS(0)iso and NICS(1)zz can be measured simultaneously.
The NICS(0)iso represents the negaꢀve of isotropic shielding
tensor, while the NICS(1)zz represents the negaꢀve of the
tensor in the zz direcꢀon. All NICS values are in ppm.
Synthesis of Fe(sma)3 (4)
A sample of Hsma (0.0631 g, 0.3338 mmol) was dissolved in 2
mL of ethanol. Fe(NO3)3• 9 H2O (0.0433 g, 0.1073 mmol) was
dissolved in 3 mL of DI water and stirred under nitrogen. The
selenomaltol mixture was added drop wise to the iron solution,
immediately forming a black precipitate. An additional 10 ml of
water was added to further facilitate precipitation. The resulting
mixture was filtered and washed with 5ml of hexanes twice and an
additional 5 ml of DI water. The solid was placed under vacuum to
dry overnight and yielded 0.0561 g (84%) of a black solid. The
compound was crystallized in CH2Cl2 by vapour diffusion with
hexane to produce samples suitable for X-ray diffraction. ESI MS:
m/z (pos.) 433.8255 (M+ - sma). Anal. calc’d for H15C18Se3O6Fe: C,
34.87; H, 2.44. Found: C, 34.95; H, 2.47.
Synthesis of selenomaltol (Hsma)
Selenomaltol was prepared by dissolving 0.4192 grams (3.324
mmol) of maltol in 15 mL of anhydrous 1,4-dioxane in a 35 mL
microwave reacꢀon vessel. Woollins reagent (0.5650 g, 1.062 mmol)
was added to the vessel, and the mixture heated in the microwave
for 30 minutes at 125 °C. Water was added to the resulꢀng black
mixture. Extracꢀon with hexane produced a dark red organic phase,
which yielded pure selenomaltol aꢂer hexane was removed via
rotavap. The resulꢀng red powder was washed with cold water and
stored as a solid. The compound was crystallized via slow
evaporaꢀon of hexanes top produce samples suitable for X-ray
diffracꢀon. Yield 0.3771 grams (60%). ESI MS: m/z (pos.) 190.9604
(M +H) 1H NMR (600 MHz, CDCl3): δ 7.68 (d,1H), 7.55 (d,1H), 2.30
(s, 3H), δ 7.83 (s, 1H). 13C NMR (600 MHz, CDCl3): δ 186, 154, 146,
145, 130, 16.
Acknowledgements
This study was supported in part by funds from the Faculty
Research Investment Program and the Vice Provost for
Research at Baylor University and the Chemical Sciences,
Geosciences, and Biosciences Division, Office of Basic Energy
Sciences, Office of Science, U. S. Department of Energy under
Award Number DE-SC0010212. We also acknowledge
departmental support from Baylor University Facilities for
Mass Spectroscopy, NMR, EPR and Crystallography. The
authors would also like to acknowledge Dr. Murugaeson
Kumar for his help on EPR data collection.
Synthesis of Zn(sma)2 (1)
A sample of Hsma (0.0610 g, 0.3194 mmol) was dissolved in 2
mL of ethanol to form a bright red solution. Zn(C2H3O2)2 (0.0293 g,
0.1597 mmol) was then dissolved in 3 ml of DI water and stirred
under nitrogen. The selenomaltol mixture was added drop wise to
the zinc solution, immediately forming a yellow precipitate. The
solution was centrifuged and the pellet washed with hexane twice
to remove any excess selenomaltol. The flask was placed under
vacuum to dry overnight and yielded 0.0467 g (79%) of an orange
solid. The compound was crystallized in CH2Cl2 by vapor diffusion
with hexane to produce samples suitable for X-ray diffraction. 1H
NMR (600 MHz, CDCl3): δ 7.87 (d,1H), 7.62(d,1H), 2.56 (s, 3H). 13
NMR (600 MHz, (CD3)2SO): δ 172, 161, 155, 146, 126, 17. ESI MS:
m/z (pos.) 442.8263(M +H).
C
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Synthesis of Ni(sma)2 (3)
6 | J. Name., 2012, 00, 1-3
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