Dalton Transactions
Page 6 of 8
DOI: 10.1039/C4DT03263B
† Electronic Supplementary Information (ESI) available: Experimental
procedures and characterization data; mass, UVꢀVis/NIR, CV. Xꢀray
60 structural parmeters and bond distance, and angles for 1. Optimized
geometry and the Cartesian coordinates of complex 1 also given. See
DOI: 10.1039/b000000x/
†† This project is funded by DST (SR/FT/CS−86/2011) and BRNS
(2012/37C/28/BRNS/1375). MKM and AKB thanks IIT Guwahati, and
65 UGC (India), respectively, for their doctoral fellowship. CM is indebted
to Prof. A. Sundaresan, JNCASR, Bangalore, India, for the SQUID
measurement. Mr. Samir Ghorai is acknowleded for Xꢀray single crystal
measurement. We thank CIF, and Department of Chemistry, IIT
Guwahati, for instrumental facilities.
temperature and filtered through a celite pad. The filtrate was
extracted with CH2Cl2 (3 × 30 mL) and the combined organic
layer was washed with water followed by brine and finally dried
over anhydrous Na2SO4. The solvent was evaporated to have a
white solid. Yield: 0.490 g, 95%. FTIR (KBr pellet, cm−1): 3457,
3417, 3357, 3340, 1611, 1584, 1570, 1477, 1446, 1315, 1289,
1255, 1157, 1138, 1030, 1018, 759, 754, 686, 675, 668, 540, 498,
5
1
464. H NMR (399.85 MHz, CDCl3): δ 7.21 (d, J = 7.6 Hz, 2H),
7.12−7.09 (m, 2H), 6.73−6.67 (m, 4H), 4.20 (s, 4H) ppm.
10 ESI−MS (+) m/z for [C12H12N2S + H]+: Calcd, 217.0794; found,
70
217.0808.
1
(a) J. Stubbe, W. A. van der Donk, Chem. Rev. 1998, 98, 705; (b) R.
H. Holm, P. Kennepohl, E. I. Solomon, Chem. Rev. 1996, 96, 2239;
(c) J. W. Whittaker, Chem. Rev. 2003, 103, 2347; (d) R. Banerjee,
Chem. Rev(Editorial), 2003, 103, 2081; (e) N. Ito, S. E. V. Phillips,
C. Stevens, Z. B. Ogel, M. J. Mcpherson, J. N. Keen, K. D. S. Yadav
and P. F. Knowles, Nature, 1991, 350, 87; (f) N. Ito, S. E. V
Phillips, K. D. S. Yadav and P. F. Knowles, J. Mol. Biol., 1994, 238,
794.
Synthesis of [C40H52N2O2S], H4LS(AP/AP). To a suspension of
bis(o−aminophenyl) sulfide (0.489 g, 2.26 mmol) in hexane (20
15 mL), 3,5−di−tert−butylcatechol (1.005 g, 4.52 mmol) was added,
followed by addition of Et3N ( 0.05 mL). The reaction mixture
was then refluxed for 30 minutes and then stirred at room
temperature (30 °C) for 5 h. A white precipitate was obtained in
due course. The solid was filtered, washed with hexane (20 mL)
20 and dried under air. Yield: 1.010 g, 71%. FTIR (KBr pellet,
cm−1): 3434, 3358, 3335, 3061, 2961, 2906, 2868, 1602, 1587,
1574, 1492, 1472, 1446, 1421, 1391, 1380, 1362, 1310, 1264,
1227, 1203, 1158, 1116, 1054, 1035, 977, 882, 824, 808, 768,
75
80
2
(a) P. Chaudhuri, K. Wieghardt, Prog. Inorg. Chem. 2001, 50, 151;
(b) P. Chaudhuri, K. Wieghardt, T. Weyhermüller, T. K. Paine, S.
Mukherjee, C. Mukherjee, Biol. Chem. 2005, 386, 1023; (c) S. Ye, B.
Sarkar, F. Lissner, T. Schleid, J. van Slageren, J. Fiedler and W.
Kaim, Angew. Chem. Int. Ed., 2005, 44, 2103; (d) R. Rakshit, S.
Ghorai, S. Biswas and C. Mukherjee, Inorg. Chem., 2014, 53, 3333.
P. Chaudhuri, C. N. Verani, E. Bill, E. Bothe, T. Weyhermüller and
K. Wieghardt, J. Am. Chem. Soc., 2001, 123, 2213.
85
3
4
5
1
750, 718, 679, 648, 636, 617, 560, 487. H NMR (600.17 MHz,
R. Metzinger, S. Demeshko, C. Limberg, Chem. Eur, J., 2014, 20,
4721.
25 CDCl3): δ 7.40ꢀ7.38 (m, 2H), 7.21 (d, J = 2.4 Hz, 2H), 7.16−7.14
(m, 2H), 6.84−6.82 (m, 2H), 6.79 (d, J = 1.8 Hz, 2H), 6.48 (d, J =
7.8 Hz, 2H), 6.09 (s, 2H), 5.90 (s, 2H), 1.41 (s, 18H), 1.20 (s,
18H) ppm. 13C NMR (100.55 MHz, CDCl3): δ 149.7, 147.2,
142.6, 135.7, 133.4, 130.0, 127.1, 122.7, 122.0, 120.3, 118.5,
30 114.8, 35.2, 34.5, 31.8, 29.7 ppm. ESI−MS (+) m/z for
[C40H52N2O2S + H]+: Calcd, 625.3822; found, 625.3820.
CCDC 993713 (1•1CH3CN) contains the supplementary
crystallographic data for this paper. These data can be obtained free
of charge from The Cambridge Crystallographic Data Centre via
molecule CH3CN was found in the molecular structure.
90
6
(a) C. Mukherjee, U. Pieper, E. Bothe, V. Bachler, E. Bill, T.
Weyhermüller, P. Chaudhuri, Inorg. Chem. 2008, 47, 8943; (b) G. A.
Abakumov, V. K.. Cherkasov, V. I. Nevodchikov, V. A. Kuropatov,
G. T. Yee, Pierpont, C. G. Inorg. Chem., 2001, 40, 2434; (c) K. J.
Blackmore, J. W. Ziller, A. F. Heyduk, Inorg. Chem. 2005, 44, 5559;
(d) C. Mukherjee, T. Weyhermüller, K. Wieghardt, P Chaudhuri,
Dalton Trans. 2006, 2169; (e) S. Ghorai, C. Mukherjee, Dalton
Trans. 2014, 43, 2169.
95
Synthesis of [CuLS(IBQ/ISQ)Cl]0•1CH3CN (1•1CH3CN). To a
suspension of H4LS(AP/AP) (0.287 g, 0.46 mmol) in CH3CN (5
35 mL), CuCl2•2H2O (0.157 g, 0.92 mmol), and Et3N (0.2 mL) were
added sequentially. The resulted reaction mixture was stirred for
24 h at room temperature (30 °C) under air when the initially
formed blueꢀgreen precipitate was gradually transformed to a
brown solid. Thus formed brown precipitate was filtered, and
40 washed with CH3CN (10 mL). Recrystallization of the solid from
a CH2Cl2/CH3CN (5:2) solvent mixture provided a cubeꢀshaped
crystalline solid suitable for singleꢀcrystal Xꢀray diffraction
study. The solid was separated and washed with CH3CN (5 mL).
Yield: 0.181 g, 52 %. FTIR (KBr pellet, cm−1): 3443, 3252, 3050,
45 2956, 2908, 2869, 2252, 1640, 1618, 1589, 1504, 1465, 1430,
1379, 1335, 1310, 1271, 1250, 1204, 1025, 899, 765, 748. ESIꢀ
MS (+) m/z for [C40H48CuN2O2S]+: Calcd, 683.2832; found,
683.2832. Anal. Calcd for C40H48ClCuN2O2S•1CH3CN: C,
66.37; H, 6.76; N, 5.53. Found: C, 66.29; H, 6.72; N, 5.39%.
100
105
110
115
7
8
(a) C. Mukherjee, U. Pieper, E. Bothe, V. Bachler, E. Bill, T.
Weyhermüller and P. Chaudhuri, Inorg. Chem. 2008, 47, 2740.
The optimization of complex 1 was performed at the B3LYP/6ꢀ31G
(d, p) level of theory employing polarizable continuum model (PCM)
(for references: (a) M. Cossi, V. Barone, J. Chem. Phys. 1998, 109,
6246. (b) J. Tomasi, M. Persico, Chem. Rev. 1994, 94, 2027. (c) M.
Cossi, V. Barone, R. Cammi, J. Tomasi, Chem. Phys. Lett. 1996, 255,
327. (d) V. Barone, M. Cossi, J. Tomasi, J. Comput. Chem. 1998, 19,
404.) using universal force field (UFF) atomic radii in acetonitrile
solvent (ε = 35.69) (for reference: A. V. Marenich, C. J. Cramer, D.
G. Truhlar, J. Phys. Chem. B 2009, 113, 6378.).
9 (a) W. Li, F. Yang, Z. Wang, Int. J. Quant. Chem., 2011, 111, 2099.
(b) S. Torres, G. Ferraudi, M. J. Aguirrea, M. Isaacsc, B. Matsuhiro,
N. P. Chandĭa, L. Mendoza, Helv. Chim. Acta, 2011, 94, 293.
10 C. Mukherjee, unpublished result.
11 G. M. Sheldrick, Acta Crystallogr., 2008, A64, 112.
12 M. Cossi, V. Barone, J. Chem. Phys. 1998, 109, 6246.
13 J. Tomasi, M. Persico, Chem. Rev. 1994, 94, 2027.
50 Notes and references
120 14 M. Cossi, V. Barone, R. Cammi, J. Tomasi, Chem. Phys. Lett. 1996,
255, 327.
a
Department of Chemistry, Indian Institute of Technology,
Guwahati,781039, Assam, India. Fax: (+) 91ꢀ361ꢀ258ꢀ2349; Tel: (+) 91ꢀ
361ꢀ258ꢀ2327; Eꢀmail:cmukherjee@iitg.ernet.in
15 V. Barone, M. Cossi, J. Tomasi, J. Chem. Phys. 1997, 107, 3210.
16 V. Barone, M. Cossi, J. Tomasi, J. Comput. Chem. 1998, 19, 404.
17 A. V. Marenich, C. J. Cramer, D. G. Truhlar, J. Phys. Chem. B 2009,
b
Computation and Simulation Unit (Analytical Discipline and
55 Centralized Instrument Facility), CSIR–Central Salt and Marine
Chemicals Research Institute, Bhavnagar–364002, India. Fax: 00–91–
278–2567562; Email: ganguly@csmcri.org
125
113, 6378.
18 A. M. Whyte, K. Awaga, B. Roach, F. J. White, D. K. Henderson, P.
Richardson, P. A. Tasker, N. Robertson, Inorg. Chem. 2011, 50,
12867.
6
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