L. Thevenin et al.
Inorganica Chimica Acta 518 (2021) 120215
2.6. Synthesis of complex 2
Table 1
Crystal data for 1⋅H2 and 2⋅py.
Under inert atmosphere, solid [Co(acac)2] (1.40 g, 5 mmol) was
added to a stirred toluene (15 mL) solution of pro-ligand 1⋅H2 (1.93 g, 5
mmol) at 0 ◦C. The resulting solution was allowed to warm up at room
temperature and further heated at 90 ◦C overnight, leading to the for-
mation of a yellow precipitate. The reaction mixture was cooled down to
room temperature and the pale yellow solid was filtered off and dried
under vacuum (1.53 g, 75% yield). Anal. Calcd for C19H15CoNO2S2
(412.39): C, 55.34; H, 3.67; N, 3.40%. Found: C, 55.10; H, 3.65; N,
3.60%. MS (ESI): m/z 413.0 [M + H]+, 430.0 [M + NH4]+. FTIR:
νmax(solid)/cmꢀ 1: 1595m, 1579s, 1557w, 1513w, 1463vs, 1455sh,
1435s, 1409m, 1312vs, 1287m, 1261m, 1238m, 1156w, 1126w, 1094w,
1029w, 1014w, 901w, 852m, 838s, 796m, 770s, 740vs, 721m, 700w,
676w, 601w, 576sh, 567m, 525s, 477m, 463m, 409s. CV: see main text
and ESI.
Identification code
1⋅H2 (CCDC 2034822)
2⋅py (CCDC 2034823)
Empirical formula
Formula weight
Temperature, K
Wavelength, Å
Crystal system
Space group
a, Å
C
19H17NO2S2
C24H20CoN2O2S2
491.46
355.45
173(2)
173.2(3)
1.54184
0.71073
Monoclinic
P21/n
Orthorhombic
Pbcn
9.5890(5)
9.1824(5)
19.2580(11)
90.0
7.8069(4)
15.4402(7)
22.4263(12)
90.0
b, Å
c, Å
◦
α,
β, ◦
92.262(2)
90.0
90.0
γ, ◦
90.0
Volume, Å3
Z
1694.35(16)
4
2703.3(2)
4
Density (calc), Mg/m3
Abs. coefficient, mmꢀ 1
F(000)
1.393
1.208
0.325
6.579
744
1012
Crystal size, mm3
Theta range, ◦
Reflections collected
0.470 × 0.180 × 0.120
2.412 to 30.033
13,224
0.45 × 0.38 × 0.16
3.942 to 61.541
5418
2.7. Synthesis of complex 2⋅py
Complex 2 (50 mg, 0.12 mmol) was dissolved in pyridine (8 mL) at
room temperature to afford a yellow solution, which was stirred over-
night at room temperature. Addition of pentane (20 mL) induced pre-
cipitation of the pyridine adduct 2⋅py, which was isolated as a light
brown powder after decanting off the mother liquor, further washing
with pentane (2 × 10 mL) and drying under vacuum (56.6 mg, 95%
yield). Anal. Calcd for C24H20CoN2O2S2 (491.49): C, 58.65; H, 4.10; N,
5.70; S, 13.05%. Found: C, 57.56; H, 3.67; N, 5.87; S, 12.07%. MS (ESI):
m/z 514.0 [M + Na]+, 412.0 [M - py]+. FTIR: νmax(solid)/cmꢀ 1: 1594m,
1578s, 1556w, 1545w, 1460vs, 1452sh, 1435s, 1408w, 1311vs, 1286m,
1260m, 1238m, 1156w, 1147w, 1125w, 1094w, 1029m, 1013m, 958w,
944w, 918w, 901m, 882w, 852m, 838s, 796m, 769s, 740vs, 721m,
700m, 676m, 600m, 577m, 566m, 526s, 476m, 463m, 408s. 1H NMR
(400 MHz, d5-pyridine): δ (ppm) 69.1 (width = 48.5 Hz, s, 1H), 65.8
(61.2 Hz, s, 1H), 52.8 (22.2 Hz, s, 1H), 47.4 (22.2 Hz, s, 1H), 10.3 (57.7
Hz, s, 13H, py), 8.9 (16.4 Hz, s, 7H, py), 8.6 (32.5 Hz, s, 13H, py), 7.3
(21.0 Hz, s, 2H), 5.1 (29.1 Hz, s, 1H), ꢀ 4.7 (17.6 Hz, s, 1H). EPR: see
Indpt reflections (Rint
)
4910 (0.0225)
99.1
2066 (0.0405)
96.2
Completeness, %
Absorption correction
Max. / min. transmission
Refinement method
Multi-scan
0.7471 and 0.6759
F2
Multi-scan
1.0 and 0.252
F2
Data /restraints/parameters
4910/0/219
1.052
2066/0/143
1.080
Goodness-of-fit on F2
R1, wR2 [I > 2
σ(I)]
0.0333, 0.0988
0.0409, 0.1046
0.418/ꢀ 0.280
0.0701, 0.1822
0.0813, 0.1908
0.934/ꢀ 0.569
R1, wR2 (all data)
Residual density, e.Åꢀ 3
the final refinement. The drawing of the molecules was realized with the
help of ORTEP32 [46,47] and POV-Ray version 3.7. Crystal data and
refinement parameters are shown in Table 1. Selected distances and
angles are reported below Figs. 1 and 3. All bond lengths and angles
(Tables S1 and S2) and hydrogen interactions (Table S3) are given in the
ESI.
Crystallographic data have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication no.
2034822–2034823. Copies of the data can be obtained free of charge on
application to the Director, CCDC, 12 Union Road, Cambridge CB2 1EZ,
UK (fax: (+44) 1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
main text and ESI. UV–Vis: λmax(pyridine)/nm: 413 (
ε
/dm3 molꢀ 1 cmꢀ 1
:
1 210).
2.8. Synthesis of complex 3
2.5. Synthesis of pro-ligand 1⋅H2
Solid I2 (90 mg, 0.39 mmol, 0.5 eq) was added all at once to a stirred
suspension of complex 2 (320 mg, 0.77 mmol, 1 eq) in 10 mL of meth-
anol at room temperature. The resulting mixture was stirred at room
temperature overnight. A dark brown precipitate formed and was iso-
lated by filtration. The latter was then washed with pentane (3 × 10 mL)
and dried under vacuum, affording a dark brown solid (315 mg, 77%
yield). Anal. Calcd for C19H15CoINO2S2 (539.29): C, 42.32; H, 2.80; N,
2.60; S, 11.89%. Found: C, 42.55; H 2.55; N, 2.75; S, 11.89%. MS (ESI):
m/z 412.0 [M - I]+. FTIR: νmax(solid)/cmꢀ 1: 1598w, 1576s, 1549m,
1462s, 1452vs, 1442sh, 1390w, 1377m, 1321sh, 1306s, 1269s, 1239m,
1184w, 1165w, 1156w, 1124m, 1092m, 1048w, 1033w, 1022m, 976w,
932w, 882m, 849s, 783m, 749s, 740vs, 701m, 677m, 644m, 606w,
579m, 536w, 465s, 434s, 416sh. 1H NMR (300 MHz, d6-DMSO): δ (ppm)
5.12 (4H, d, 4J = 6.1 Hz, CH2), 6.46 (2H, d, 3J = 8.4 Hz, Harom), 6.56
Pure 2-mercaptophenol (4.51 g, 3.6 mL, 35.8 mmol, 2 eq) was slowly
added to a solution of 2,6-di(chloromethyl)pyridine (3.15 g, 17.9 mmol,
1 eq) in 180 mL of deoxygenated ethanol. Sodium hydroxide (1.43 g,
35.8 mmol, 2 eq) and water (18 mL) were then added and the resulting
solution was stirred overnight at room temperature. The resulting
colorless precipitate was isolated by filtration and dried under reduced
pressure. Recrystallization from an acetone/H2O mixture afforded 1⋅H2
as colorless needles (5.15 g, 81% yield). Anal. Calcd for C19H17NO2S2
(355.47): C, 64.20; H, 4.82; N, 3.94; S, 18.04%. Found: C, 63.88; H,
4.66; N, 3.94; S, 17.61%. MS (ESI): m/z 356.0 [M + H]+. FTIR:
νmax(solid)/cmꢀ 1: 3480br, 3137br, 1593m, 1574m, 1492w, 1467s,
1453s, 1401m, 1356w, 1293s, 1251s, 1223w, 1217w, 1173m, 1152s,
1027m, 1011m, 945w, 938w, 888m, 865m, 834m, 808m, 753vs, 732sh,
713m, 677m, 611m. 1H NMR (400 MHz, d6-DMSO): δ (ppm) 4.21 (4H, s,
CH2), 6.71 (2H, dt, 3J = 7.6 Hz, 4J = 1.2 Hz, Harom), 6.84 (2H, dd, 3J =
8.0 Hz, 4J = 1.6 Hz, Harom), 7.04 (2H, dt, 3J = 8.0 Hz, 4J = 1.6 Hz, Harom),
7.20 (2H, dd, 3J = 8.0 Hz, 4J = 1.6 Hz, Harom), 7.25 (2H, d, 3J = 7.6 Hz,
3
3
(2H, pseudo t, J = 7.4 Hz, Harom), 6.85 (2H, pseudo t, J = 7.7 Hz,
H
arom), 7.60 (2H, d, 3J = 7.7 Hz, Harom), 7.79 (1H, d, 3J = 7.4 Hz, Harom),
7.82 (2H, d, 3J = 8.4 Hz, Harom). 1H NMR (400 MHz, CDCl3): δ (ppm)
4.73 and 5.19 (4H, AX spin system, 2J = 16 Hz, CH2), 6.64 (4H, m,
H
arom), 6.92 (2H, pseudo t, 3J = 7.6 Hz, Harom), 7.39 (2H, d, 3J = 7.6 Hz,
arom), 7.69 (1H, t, 3J = 8.0 Hz, Harom), 9.98 (2H, s, br, OH). 13C{1H}
Harom), 7.62 (1H, pseudo t, 3J = 7.6 Hz, Harom), 7.67 (2H, d, 3J = 6.8 Hz,
H
H
arom). 13C{1H} NMR (101 MHz, d6-DMSO): δ (ppm) 55.6 (CH2), 113.6
NMR (101 MHz, d6-DMSO): δ (ppm) 37.5 (CH2), 115.5 (CHarom), 120.0
(CHarom), 121.8 (Cquat), 122.1 (CHarom), 128.0 (CHarom), 130.4 (CHarom),
138.7 (CHarom), 155.9 (Cquat), 157.3 (Cquat).
(Cquat), 115.5 (CHarom), 120.1 (CHarom), 122.2 (CHarom), 130.4 (CHarom),
131.4 (CHarom), 138.5 (CHarom, para-N), 159.6 (Cquat), 173.8 (Cquat).
UV–Vis: λmax(CH2Cl2)/nm: 417 (
ε
/dm3 molꢀ 1 cmꢀ 1: 2 440), 535sh.
3