Organic & Biomolecular Chemistry
Paper
Lb (o,o), red powder (65%). 1H NMR (400 MHz, CD2Cl2): was refluxed overnight. Then the solvent was removed and the
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8.68 (d, J = 5.0 Hz, 2H, Py), 8.42 (s, 2H, Py), 7.52 (d, J = 9.0 crude was dissolved in a minimal amount of CH2Cl2. After fil-
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Hz, 4H, C6H4), 7.30 (s, 2H, Thio), 7.20 (dd, J = 5.3 Hz, J = 1.6 tration over celite, a recrystallization was performed with a
Hz, 2H, Py), 7.01 (m, 3J = 15.9 Hz, 4H, vCH and Thio), 6.75 (d, mixture of pentane–CH2Cl2 to afford LbRe(o,o) as a violet
3J = 15.9 Hz, 2H, vCH), 6.71 (d, 3J = 9.0 Hz, 4H, C6H4), 3.37 (t, powder (140 mg, 75%). 1H NMR (400 MHz, CD2Cl2): 8.88 (d,
3J = 7.6 Hz, 8H, N–CH2), 2.00 (s, 6H, CH3), 1.88 (s, 6H, CH3), 3J = 5.92 Hz, 2H, Py), 7.99 (s, 2H, Py), 7.56 (d, J = 8.55 Hz, 4H,
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1.64 (m, 8H, N–CH2–CH2), 1.42 (m, 8H, CH2–CH3), 1.02 (t, J = C6H4), 7.35 (s, 2H, Thio), 7.37 (dd, J = 5.9 Hz, J = 1.4 Hz, 2H,
7.4 Hz, 12H, CH2–CH3). 13C[1H] NMR (100 MHz, CD2Cl2): Py), 7.06 (d, 3J = 15.8 Hz, 2H, vCH), 6.84 (s, 2H, Thio), 6.73 (d,
156.23 (Py), 149.49 (Py), 148.60 (C6H4), 146.43, 144.57, 140.27, 3J = 8.52 Hz, 4H, C6H4), 6.67 (d, J = 15.77 Hz, 2H, vCH), 3.38
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138.66, 138.12, 128.12, 126.89, 126.31, 124.98, 123.83, 123.64, (m, 8H, N–CH2), 2.07 (s, 6H, CH3), 1.87 (s, 6H, CH3), 1.65 (m,
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120.63, 119.97, 119.43, 117.76, 111.60, 50.68, 29.37, 20.28, 8H, N–CH2–CH2), 1.43 (sext, J = 7.52 Hz, 8H, CH2–CH3), 1.02
14.41, 13.96, 13.75. HRMS: m/z 1369.41839 [M+Na]+ calcd for (t, 3J = 7.3 Hz, 12H, CH2–CH3). 13C[1H] NMR (100 MHz,
C72H70N4F12NaS4, 1369.4186; m/z 1347.43645 [M + H]+ calcd CD2Cl2): 197.35, 189.14, 155.82, 152.46, 148.98, 148.63, 147.10,
for C72H71N4F12S4 1347.4357. Anal. Calcd for C72H70F12N4S4, 140.89, 139.05, 136.35, 130.13, 127.23, 127.10, 124.47, 123.59,
CH2Cl2: C, 61.21; H, 5.07; N, 3.91, measured C, 61.23; H, 4.99; 123.06, 121.84, 120.63, 120.45, 119.05, 111.64, 50.69, 29.36,
N, 4.08.
20.26, 14.97, 14.00, 13.70. Elemental analysis: calcd for
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Lc (o,o), brown powder (61%). H NMR (500 MHz, CD2Cl2): C75H73N4O3F12S4BrRe·3CH2Cl2: C, 47.91; H, 4.07; N, 2.87; S,
8.70 (d, 3J = 5.1 Hz, 2H, Py), 8.44 (s, 2H, Py), 7.64 (d, 3J = 6.56. Found: C, 47.81; H, 4.11; N, 2.63; S, 6.36.
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8.7 Hz, 4H, Ph), 7.41 (s, 2H, Thio), 7.23 (dd, J = 5.1 Hz, J =
1.6 Hz, 2H, Py), 7.01 (d, J = 15.9 Hz, 2H, vCH), 7.00 (d, J =
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8.7 Hz, 6H, C6H4 and Thio), 6.81 (d, J = 15.9 Hz, 2H, vCH),
Acknowledgements
3.90 (s, 6H, OCH3), 2.00 (s, 6H, CH3), 1.88 (s, 6H, CH3). 13C[1H]
NMR (125 MHz, CDCl3): 160.31, 156.38, 149.64, 145.05, 144.67, This work was supported by the Agence Nationale de la
140.13, 139.89, 138.68, 132.07, 128.33, 127.37, 127.15, 125.76, Recherche (ANR COMET Blan08-1-308898) and LIA CHILI MIF.
125.08, 124.01, 123.81, 122.22, 120.77, 118.41, 114.71, 55.59, LEA Rennes-Durham is also acknowledged.
29.84, 14.93, 14.80, 14.31. Elemental analysis: calcd for
C58H40N2O2F12S4·CH2Cl2: C, 57.23; H, 3.42; N, 2.26. Found: C,
57.56; H, 3.55; N, 2.40.
References
Synthesis of LbZn(o,o)
1 V. Guerchais, L. Ordronneau and H. Le Bozec, Coord.
In a Schlenk tube under argon, ligand Lb (o,o) (100 mg,
0.1 mmol, 1 eq.) and Zn(OAc)2·2H2O (16.3 mg, 0.1 mmol,
1 eq.) were dissolved in CH2Cl2 (8 mL). The mixture was stirred
at r.t. overnight. Then, the solvent was removed and the crude
was dissolved in a minimum of CH2Cl2. Pentane was added to
precipitate LbZn(o,o) as red crystals (105 mg, 93%). 1H NMR
(400 MHz, CD2Cl2): 8.83 (d, 3J = 5.4 Hz, 2H, Py), 7.99 (s, 2H,
Chem. Rev., 2010, 254, 2533–2545.
2 M. Irie, Chem. Rev., 2000, 100, 1685–1716.
3 A. Perrier, F. Maurel and D. Jacquemin, Acc. Chem. Res.,
2012, 45, 1173–1182.
4 C.-C. Ko and and V. W.-W. Yam, J. Mater. Chem., 2010, 20,
2063–2070.
5 V. Aubert, V. Guerchais, E. Ishow, K. Hoang-Thi, I. Ledoux,
K. Nakatani and H. Le Bozec, Angew. Chem., Int. Ed., 2008,
47, 577–580.
6 (a) V. Aubert, L. Ordronneau, M. Escadeillas, J. A. G.
Williams, A. Boucekkine, E. Coulaud, C. Dragonetti,
S. Righetto, D. Roberto, R. Ugo, A. Valore, A. Singh,
I. Ledoux-Rak, J. Zyss, H. Le Bozec and V. Guerchais, Inorg.
Chem., 2011, 50, 5027–5038; (b) L. Ordronneau, V. Aubert,
R. Métivier, E. Ishow, J. Boixel, K. Nakatani, F. Ibersiene,
D. Hammoutène, A. Boucekkine, H. Le Bozec and
V. Guerchais, Phys. Chem. Chem. Phys., 2012, 14, 2599–
2605; (c) L. Ordronneau, H. Nitadori, I. Ledoux, A. Singh,
J. A. G. Williams, M. Akita, V. Guerchais and H. Le Bozec,
Inorg. Chem., 2012, 51, 5627–5636; (d) H. Nitadori,
L. Ordronneau, J. Boixel, D. Jacquemin, A. Boucekkine,
A. Singh, M. Akita, I. Ledoux, V. Guerchais and H. Le
Bozec, Chem. Commun., 2012, 48, 10395–10397;
(e) L. Ordronneau, V. Aubert, V. Guerchais, A. Boucekkine,
H. Le Bozec, A. Singh, I. Ledoux and D. Jacquemin, Chem.–
Eur. J., 2013, 19, 5845–5849.
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Py), 7.54 (d, J = 8.8 Hz, 4H, Ph), 7.50 (d, J = 5.7 Hz, 2H, Py),
7.34 (s, 2H, Thio), 7.08 (d, 3J = 15.8 Hz, 2H, vCH), 6.87 (s, 2H,
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thio), 6.77 (m, 2H, vCH), 6.72 (d, J = 8.9 Hz, 4H, Ph), 3.37 (t,
3J = 7.1 Hz, 8H, N–CH2), 2.09 (s, 6H, OAc), 2.02 (s, 6H, CH3),
1.89 (s, 6H, CH3), 1.64 (m, 8H, N–CH2–CH2), 1.41 (sext, 3J = 7.6
Hz, 8H, CH2–CH3), 1.01 (t, 3J = 7.3 Hz, 12H, CH2–CH3). 13C[1H]
NMR (100 MHz, CD2Cl2): 179.95 (CvO), 149.49, 149.33,
148.91, 148.75, 148.29, 140.93, 138.96, 136.48, 129.98, 127.06,
124.53, 123.64, 121.65, 120.43, 119.04, 118.60, 111.60, 50.68,
29.36, 21.77, 20.26, 14.64, 14.07, 13.72. HRMS: m/z 1551.37415
[M + Na]+ calcd for C76H76N4O4F12NaS464Zn 1551.3739; m/z
1469.37107 [M
−
OAc]+ calcd for C74H73N4O2F12S464Zn
1469.3707. Anal. Calcd for C76H76N4F12O2S4Zn·0.5CH2Cl2: C,
58.39; H, 4.93; N, 3.56; S, 8.15. Found: C, 58.21; H, 5.07; N,
3.77; S, 7.88.
Preparation of LbRe(o,o)
In a Schlenk tube under argon, ligand Lb (o,o) (1 eq.) and Re-
(CO)5Br (1 eq.) were dissolved in toluene (15 mL). The mixture
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