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Chemical Science
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ARTICLE
Journal Name
1
Linkage: Structural Significance DiOnI: 10C.1h0e3Vm9ie/wiCs8AtrrStyiCcl0e5O8an1ln9inAde
Biotechnology and Materials Science, John Wiley & Sons, Ltd.,
2003.
H. Lundberg, F. Tinnis, N. Selander and H. Adolfsson, Chem.
Soc. Rev., 2014, 43, 2714-2742.
J. M. García, F. C. García, F. Serna and J. L. de la Peña, Prog.
Polym. Sci., 2010, 35, 623-686.
R. Das, G. S. Kumar and M. Kapur, Eur. J. Org. Chem., 2017,
5439-5459.
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5502.
R. P. Houghton and R. R. Puttner, J. Chem. Soc. D, 1970, 1270-
1271.
mixed to form precipitate, immediately. The supernatant was
removed by using cannula, and the residues were extracted
with toluene, and layered with methanol to induce
recrystallization. M = Fe: Deep red solid, 1.09 g, 0.900 mmol,
80% yield, M = Co: Burgundy solid, 152 mg, 0.124 mmol, 64%
yield, M = Cu: Deep blue solid, 22.2 mg, 20.0 mol, 11% yield.
2
3
4
5
6
7
8
9
Synthesis of [Mn(dbm)(OMe)(MeOH)]4 (1b):30a MnCl2 (629
mg, 5.00 mmol) and dibenzoylmethane (1.12 g, 5.00 mmol, 1.0
equiv) were dissolved in 10 mL of methanol. To another flask,
KOMe (10 mmol, 2.0 equiv) was dissolved in methanol. Two
solutions were slowly mixed, and yellow powder was
immediately precipitated. The supernatant was removed by
using cannula, and the residues were extracted with toluene,
and layered with methanol to induce recrystallization to give 1b
as orange solid (258 mg, 0189 mmol, 15% yield).
M. C. Bröhmer, S. Mundinger, S. Bräse and W. Bannwarth.
Angew. Chem., Int. Ed., 2011, 50, 6175-6177.
A. J. Kirby, I. V. Komarov, P. D. Wothers and N. Feeder, Angew.
Chem., Int. Ed., 1998, 37, 785-786.
M. Szoztak and J. Aubé, Chem. Rev., 2013, 113, 5701-5765.
10 (a) L. E. Fisher, J. M. Caroon, S. R. Stabler, S. Lundberg, S. Zaidi,
C. M. Sorensen, M. L. Sparacino and J. M. Muchowski, Can. J.
Chem., 1994, 72, 142-145; (b) X. Chen, S. Hu, R. Chen, J. Wang,
M. Wu, H. Guo and S. Sun, RSC Adv., 2018, 8, 4571-4576.
11 S. M. A. H. Siddiki, A. S. Touchy, M. Tamura and K. Shimizu,
RSC Adv., 2014, 4, 35803-35807.
12 Y. Kita, Y. Nishii, A. Onoue and K. Mashima, Adv. Synth. Catal.,
2013, 355, 3391-3395.
13 B. N. Atkinson and J. M. J. Williams, Tetrahedron Lett., 2014,
55, 6935-6938.
14 T. Deguchi, H.-L. Xin, H. Morimoto and T. Ohshima, ACS Catal.,
2017, 7, 3157-3161.
15 L. Hie, N. F. Fine Nathel, T. K. Shah, E. L. Baker, X. Hong, Y.-F.
Yang, P. Liu., K. N. Houk and N. K. Garg, Nature, 2015, 524, 79-
83.
16 L. Hie, E. L. Baker, S. M. Anthony, J.-N. Desrosiers, C.
Senanayake and N. K. Garg, Angew. Chem., Int. Ed., 2016, 55,
15129-15132.
17 J. E. Dander and N. K. Garg, ACS Catal., 2017, 7, 1413-1423.
18 Y. Bourne-Branchu, C. Gosmini and G. Daunon, Chem. Eur. J.,
2017, 23, 10043-10047.
19 X. Li and G. Zou, Chem. Commun., 2015, 51, 5089-5092.
20 G. Meng and M. Szostak, Org. Lett., 2015, 17, 4364-4367.
21 C. Liu and M. Szostak, Chem. Eur. J., 2017, 23, 7157-7173.
22 J. Hu, M. Wang, X. Pu and Z. Shi, Nat. Commun. 2017, 8, 14993.
23 S.-C. Lee, L. Guo, H. Yue, H.-H. Liao and M. Rueping, Synlett,
2017, 28, 2594-2598.
24 A. Dey, S. Sasmal, K. Seth, G. K. Lahiri and D. Maiti, ACS Catal.
2017, 7, 433-437.
25 J. A. Walker Jr., K. L. Vickerman, J. N. Humke and L. M. Stanley,
J. Am. Chem. Soc., 2017, 139, 10228-10231.
26 C. W. Cheung, J.-A. Ma and X. Hu, J. Am. Chem. Soc., 2018,
140, 6789-6792.
27 Y. Nishii, S. Akiyama, Y. Kita and K. Mashima, Synlett, 2015, 26,
1831-1834.
28 Y. Nishii, T. Hirai, S. Fernandez, P. Knochel and K. Mashima,
Eur. J. Org. Chem., 2017, 5010-5014.
Synthesis of [Mn(acac)(OEt)(EtOH)]4 (1c): MnCl2 (629 mg,
5.00 mmol) and acetylacetone (0.530 mL, 5.00 mmol, 1.0 equiv)
were dissolved in 10 mL of ethanol. To another flask, LiOEt (10
mmol, 2.0 equiv) was dissolved in ethanol. Two solutions were
slowly mixed, and yellow powder was immediately precipitated.
The supernatant was removed by using cannula, and the
residues were extracted with toluene, and layered with ethanol
to induce recrystallization to give 1c as pale yellow solid (1.00 g,
1.02 mmol, 82% yield). m.p. 282-290 °C (dec.), Anal. Calcd for
C36H72O16Mn4: C, 44.09; H, 7.40; found: C, 43.96; H, 7.69.
Synthesis of Mn(II) alkoxide-bridged binuclear complex 6c:
A solution of 1c (99.6 mg, 0.101 mmol) and 1,10-phenanthroline
(73.2 mg, 0.406 mmol, 4.00 equiv) in toluene (10 mL) was
heated at 100 °C for 18 hours under an argon atmosphere.
Then, the residues were extracted with toluene (20 mL) at 100
°C, and solution was slowly cooled to -20 °C. The supernatant
was removed by using cannula, and the resulted solid was dried
under reduced pressure to give deep red solid (71.3 mg, 0.0940
mmol, 47% yield). m.p. 230-234 °C (dec.), Anal. Calcd for
C38H40N4O6Mn2: C, 60.16; H, 5.31; N, 7.39; found: C, 60.10; H,
5.27; N, 7.14.
X-Ray Crystallographic Analyses: Crystals of 1c and 6c were
handled similarly. The crystal was mounted on the CryoLoop
(Hampton Research Corp.) with a layer of light mineral oil and
placed in a nitrogen stream at 113(1) K. Measurements were
made on Rigaku XtaLAB P200 system with graphite-
monochromated Mo–K (0.71075 Å) radiation. The structures
of complexes 1c and 6c were solved by direct methods (SIR92)39
in CrystalClear program.40 The structures were refined on F2 by
full-matrix least-squares method, using SHELXL-2013.41 H-
atoms were included in the refinement on calculated positions
riding on their carrier atoms. The function minimized was
29 T. Toyano, M. N. Rashed, Y. Morita, T. Kamichi, S. M. A. H.
Siddiki, M. A. Ali, A. S. Touchy, K. Kon, Z. Maeno, K. Yoshizawa
and K. Shimizu, ChemCatChem, 2019, 11, 449-456.
30 (a) L. E. Pence, A. Caneschi and S. J. Lippard, Inorg. Chem.,
1996, 35, 3069-3072; (b) K. L. Taft, A. Caneschi, L. E. Pence, C.
D. Delfs, G. C. Papaefthymiou and S. J. Lippard, J. Am. Chem.
Soc., 1993, 115, 11753-11766.
31 J. F. Berry, F. A. Cotton, C. Y. Liu, T. Lu, C. A. Murillo, B. S.
Tsukerblat, D. Villagrán and X. Wang, J. Am. Chem. Soc., 2005,
127, 4895-4902.
2
2 2
2
[w(Fo - Fc ) ] (w = 1 / [2 (Fo ) + (aP)2 + bP]), where P =
(Max(Fo ,0) + 2Fc ) / 3 with 2(Fo ) from counting statistics. The
function R1 and wR2 were (||Fo| - |Fc||) / |Fo| and [w(Fo
- Fc ) / (wFo )]1/2, respectively. Crystal data and structure
refinement parameters are listed Table S1. The ORTEP-3
program was used to draw the molecule.42
2
2
2
2
2 2
4
32 W. H. Watson and W. W. Holley, Croat. Chem. Acta, 1984, 57,
467-476.
Note and References
8 | J. Name., 2012, 00, 1-3
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