Inorganic Chemistry
Article
package (revision A0.2).43 The model complexes were fully optimized.
The standard 6-31G*basis set was used for hydrogen, carbon, and
nitrogen atoms and the aug-CC-pvDZ basis set for sulfur and oxygen
atoms of the bridging ligands. The SDD basis set, together with the
SDD pseudopotential, was used for the heavy-metal molybdenum
atoms. Time-dependent DFT calculations were carried out to obtain
60 excitations for all of the model compounds. By replacement of the
p-anisyl groups on [Mo2(DAniF)3]+ with hydrogen atoms, the
employed calculation models have [Mo2(NHCHNH)3]+ units as
building blocks. This simplification has been successfully used in the
Mo2 analogues.2a,b,12,21
Preparation of [O2 −(2,6-naph)−O2 ]. Complex
Mo2(DAniF)3(O2CCH3) (0.25 mmol) and 2,6-naphthalenedicarbox-
ylic acid (0.125 mmol) were mixed and dissolved in 30 mL of
tetrahydrofuran (THF). The solution was stirred at room temperature
for 5 h. The solvent was evaporated under reduced pressure. The
residue was washed with ethanol (3 × 15 mL). The product was
collected by filtration and dried under vacuum. Yield of [O2−(2,6-
naph)−O2]: 0.18 g (68%). 1H NMR (CDCl3): δ 8.49 (s, 2H,
−NCHN−), 8.40 (s, 4H,−NCHN−), 8.80 (s, 2H, aromatic H), 8.41
(d, 2H, aromatic H), 8.01 (d, 2H, aromatic H), 6.65 (d, 16H, aromatic
H), 6.58 (d, 16H, aromatic H), 6.46 (d, 8H, aromatic H), 6.26 (d, 8H,
aromatic H), 3.73 (s, 24H, −OCH3), 3.68 (s, 12H, −OCH3). UV−vis
[λmax, nm (ε, M−1 cm−1)]: 460 (5.4 × 103), 618 (2.6 × 104). Anal.
Calcd for C102H96Mo4N12O16: C, 57.52; H, 4.51; N, 7.89. Found: C,
56.98; H, 4.562; N, 7.93.
AUTHOR INFORMATION
Corresponding Author
■
Author Contributions
†These authors contributed equally.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful to the National Science Foundation of China
(Grants 21371074 and 90922010) and Jinan University for
financial support.
REFERENCES
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General Procedure for the Preparation of [OS−(2,6-naph)−
OS] and [S2−(2,6-naph)−S2]. A solution of sodium methoxide (0.50
mmol) in 10 mL of methanol was transferred to a solution of
Mo2(DAniF)3(O2CCH3) (0.25 mmol) and 2,6-dithionaphthalenedi-
carboxylic acid (or 2,6-tetrathionaphthalenedicarboxylic acid; 0.125
mmol) in 30 mL of THF. The mixture was stirred at room
temperature for 5 h. The solvent was evaporated under reduced
pressure. The residue was dissolved using 15 mL of CH2Cl2 and
filtered off through a Celite-packed funnel. The filtrate was evaporated
under reduced pressure. The residue was washed with ethanol (3 × 15
mL) and collected by filtration. The product was dried under vacuum.
1
[OS−(2,6-naph)−OS]. Yield: 0.13 g (61%). H NMR (CDCl3): δ
8.50 (s, 2H, −NCHN−), 8.35 (s, 4H, −NCHN−), 8.70 (s, 2H,
aromatic H), 8.39 (d, 2H, aromatic H), 7.89 (d, 2H, aromatic H), 6.64
(d, 16H, aromatic H), 6.58 (d, 16H, aromatic H), 6.42 (d, 8H,
aromatic H), 6.10 (d, 8H, aromatic H), 3.72 (s, 24H, −OCH3), 3.66
(s, 12H, −OCH3). UV−vis [λmax, nm (ε, M−1 cm−1)]: 460 (5.4 × 103),
618 (2.6 × 104). Anal. Calcd for C102H96Mo4N12O14S2: C, 56.65; H,
4.44; N, 7.77. Found: C, 56.88; H, 4.62; N, 7.852.
1
[S2−(2,6-naph)−S2]. Yield: 0.13 g (61%). H NMR (CDCl3): δ
8.47 (s, 2H, −NCHN−), 8.33 (s, 4H, −NCHN−), 8.75 (s, 2H,
aromatic H), 8.53 (d, 2H, aromatic H), 7.87 (d, 2H, aromatic H), 6.65
(d, 16H, aromatic H), 6.61 (d, 8H, aromatic H), 6.53 (d, 8H, aromatic
H), 6.45 (d, 8H, aromatic H), 6.24 (d, 4H, aromatic H), 6.18 (d, 4H,
aromatic H), 3.73 (s, 12H, −OCH3), 3.72 (s, 12H, −OCH3), 3.68 (s,
6H, −OCH3), 3.66 (s, 6H, −OCH3). UV−vis [λmax, nm (ε, M−1
cm−1)]: 460 (5.4 × 103), 618 (2.6 × 104). Anal. Calcd for
C102H96Mo4N12O12S4: C, 55.82; H, 4.38; N, 7.66. Anal. Calcd for
C102H96Mo4N12O12S4: C, 55.82; H, 4.38; N, 7.66. Found: C, 56.08; H,
4.52; N, 7.82.
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ASSOCIATED CONTENT
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* Supporting Information
The Supporting Information is available free of charge on the
(19) Cotton, F. A.; Liu, C. Y.; Murillo, C. A.; Villagran
J. Am. Chem. Soc. 2003, 125, 13564.
(20) Richardson, D. E.; Taube, H. Inorg. Chem. 1981, 20, 1278.
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, D.; Wang, X.
Syntheses, 1H NMR data, DPV figures, electronic
spectra, EPR figures, and computational data (PDF)
Crystallographic information in CIF format (CIF)
(21) Cotton, F. A.; Donahue, J. P.; Murillo, C. A.; Per
Chem. Soc. 2003, 125, 5486.
́
ez, L. M. J. Am.
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