mixture was neutralized with a concentrated HCl solution. The
product was extracted with dichloromethane. The combined
organic layers were dried with MgSO4 and evaporated under
vacuum to yield 4.03 g of a solid off-white product (91%).
δH [199.56 MHz, CDCl3, 298 K] 7.31 (m, 4H, phenyl ring), 3.88
(d, 3J = 7.2 Hz, 4H, –CH2–), 1.89 (t, 3J = 7.2 Hz, 2H, –SH ). δC
[50.18 MHz, CDCl3, 298 K] 138.50 (Ph–C1, Ph–C2), 129.54
(Ph–C3, Ph–C6), 127.70 (Ph–C4, Ph–C5), 25.95 (–CH2–).
1.18 mmol). The mixture was refluxed for 1 hour, then the
unreacted [Ni(acac)2] was removed by filtration and the volume
of the filtrate was reduced in vacuo to 10 ml. The dark green
product was collected in a yield of 0.170 g (71%). Crystals suit-
able for X-ray diffraction were obtained from CHCl3/Et2O.
δH [300.13 MHz, CDCl3, 300 K] 7.28 (m, 2H, Ph–H3, Ph–H6),
7.19 (m, 2H, Ph–H4, Ph–H5), 3.83 (s, 4H, Ph–CH2–S–), 2.22
(s, 4H, –C(CH3)2–CH2–S–), 1.69 (s, 12H, CH3). νmax/cmϪ1
2954m, 2887m, 2820m, 1433m, 1455s, 1362s, 1248m, 1133s,
1074s, 949m, 788s, 771s, 702s, 605m, 492s, 465s, 390m, 360s,
341s cmϪ1 (Found: C, 47.33; H, 6.13; S, 30.82. C16H24NiS4
requires C, 47.65; H, 6.00; S, 31.80%). ESI-MS: 404 = [M ϩ
H]ϩ.
ꢀ,ꢀЈ-Bis(3-hydroxy-3-methyl-1-thiabutyl)-o-xylene (6). In
80 ml ethanol 5 (3.59 g, 21.1 mmol) and 1-chloro-2-methyl-2-
propanol (4.58 g, 42.2 mmol) were dissolved. While cooling on
ice, a solution of NaOH (1.68 g, 42.2 mmol) in 10 ml water was
added. After one hour stirring, the product was worked up in a
similar way as described for 1, resulting in a yellow oil in a yield
of 6.62 g (100%). δH [199.56 MHz, CDCl3, 298 K] 7.26 (m, 4H,
phenyl ring), 3.98 (s, 4H, Ph–CH2–S–), 2.66 (s, 4H, –S–CH2–
C(CH3)2–), 2.38 (s, 2H, OH ), 1.28 (s, 12 H, CH3). δC [50.18
MHz, CDCl3, 298 K] 135.96 (Ph–C1, Ph–C2), 130.30 (Ph–C3,
Ph–C6), 127.03 (Ph–C4, Ph–C5), 70.52 (–CH2–C(CH3)2–OH),
45.59 (–S–CH2–C(CH3)2–OH), 35.17 (Ph–CH2–S–), 28.37
(CH3).
Crystal structure determinations
X-Ray intensities were measured on a Nonius KappaCCD
diffractometer with rotating anode (λ = 0.71073 Å) at a
temperature of 150(2) K. The structures were solved with
automated Patterson methods (DIRDIF9727) and refined with
SHELXL-9728 against F 2 of all reflections. Molecular illus-
tration, structure checking and calculations were performed
with the PLATON29 package.
ꢀ,ꢀЈ-Bis(3-chloro-2,2-methyl-1-thiapropyl)-o-xylene (7). The
product was synthesized in the same way as 2, resulting in a
yellow oil in a yield of 7.40 g (100%). δH [199.56 MHz, CDCl3,
298 K] 7.26 (m, 4H, phenyl ring), 4.02 (s, 4H, Ph–CH2–S–), 2.90
(s, 4H, –S–C(CH3)2–CH2–Cl), 1.62 (s, 12 H, CH3). δC [50.18
MHz, CDCl3, 298 K] 136.02 (Ph–C1, Ph–C2), 130.71 (Ph–C3,
Ph–C6), 127.44 (Ph–C4, Ph–C5), 70.23 (–S–C(CH3)2–CH2–Cl),
47.34 (–S–C(CH3)2–CH2–Cl), 35.64 (Ph–CH2–S–), 31.41
(CH3).
Ni(bsms)2. The crystals were obtained as brown hexagons.
The absorption correction was based on multiple measured
reflections (program PLATON29 routine MULABS, 0.76–0.81
transmission). Non-hydrogen atoms were refined freely with
anisotropic displacement parameters. Hydrogen atoms were
refined as rigid groups.
Ni(xbsms). The crystals were obtained as dark red blocks.
The absorption correction was based on multiple measured
reflections (program PLATON29 routine MULABS, 0.75–0.83
transmission). Non-hydrogen atoms were refined freely with
anisotropic displacement parameters. Hydrogen atoms were
refined as rigid groups.
CCDC reference numbers 174229 and 174230.
lographic data in CIF or other electronc format.
ꢀ,ꢀЈ-Bis(3-thiouronium-2,2-methyl-1-thiapropyl)-o-xylene
dihydrochloride (8). The product was synthesized in the same
way as 4, resulting in a white solid in a yield of 9.05 g (85%).
δH [199.56 MHz, D2O, 298 K] 7.36 (m, 4H, phenyl ring), 4.80
(s, –S–C(NH2)2ϩClϪ and H2O), 4.05 (s, 4H, Ph–CH2–S–), 3.48
(s, 4H, –S–C(CH3)2–CH2–), 1.54 (s, 12 H, CH3).
ꢀ,ꢀЈ-Bis(3-mercapto-2,2-methyl-1-thiapropyl)-o-xylene
(H2xbsms). This reaction was performed in a similar manner
to that of Hbsms, except that this reaction was performed in
an inert atmosphere preventing thiol oxidation to disulfide.
δH [199.56 MHz, CDCl3, 298 K] 7.23 (m, 4H, phenyl ring), 3.86
(s, 4H, Ph–CH2–S–), 2.79 (d, 3J = 8.2 Hz, 4H, –C(CH3)2–CH2–
SH), 1.66 (t, 3J = 8.2 Hz, 2H, –SH ), 1.42 (s, 12H, CH3).
Acknowledgements
Professor Jan Reedijk is gratefully acknowledged for fruitful
discussions. Dr G.A. van der Marel and Dr D.V. Fillippov
are gratefully acknowledged for discussions concerning the
mechanism of rearrangement.
References
[Ni(bsms)2]. To a suspension of [Ni(acac)2] (0.52 g, 2.02
mmol) in 35 ml ethanol was added two equivalents of 3 (1.18 g,
4.05 mmol). After the addition of two equivalents of NMe4OH
(0.73 g, 4.05 mmol), the solution was refluxed for 2 hours.
The formed crude brown product was collected by filtration and
purified by refluxing for 1 hour in 15 ml ethanol to remove
additional amounts of impurities. The product was isolated and
dried under vacuum to yield 0.58 g (60%) of a brown powder.
Crystals suitable for X-ray diffraction were obtained from the
filtrate upon standing. δH [300.13 MHz, CDCl3, 300 K] 7.36 (d
3J = 6.9 Hz, 4H, Ph–C2, Ph–C6), 7.20 (m, 6H, Ph–C3, Ph–C4,
Ph–C5), 4.02 (s, 4H, Ph–CH2–S–), 2.31 (s, 4H, C(CH3)2–CH2–
S–), 1.35 (s, 12H, CH3). νmax/cmϪ1 = 2960w, 2908m, 1495m,
1454m, 1406m, 1382m, 1364m, 1261m, 1196w, 1140m, 1081m,
1029w, 954w, 916w, 892w, 858m, 756m, 698s, 599w, 499w, 461s,
391s, 326w cmϪ1 (Found: C, 55.17; H, 6.66; S, 26.29; Ni, 12.68.
C22H30NiS4 requires C, 54.88; H, 6.28; S, 26.64; Ni, 12.21%).
ESI-MS: 481 = [M ϩ H]ϩ.
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1279