Inorganic Chemistry
Article
DCTB): m/z = 906 [4]+. IR (KBr, cm−1): ν = 1667, 1577, 1385, 1215,
1158, 1070, 799, 717, 686, 553. UV−vis (DMF, nm): νmax = 400.
Complex [Co2(NS,NS)2] 5 by Transmetalation from 3.
Complex [Zn2(NS,NS)2] 3 (49 mg, 0.06 mmol) was dissolved in
DMF (20 mL), and cobalt(II)acetate (27 mg, 0.15 mmol) dissolved in
MeOH (10 mL) was added dropwise. After the reaction mixture
stirred at ambient temperature for 12 h, n-hexane was added to
precipitate the brown complex [Co2(NS,NS)2] 5. The brown solid was
isolated by filtration and dried in vacuo. Yield: 32 mg (0.04 mmol,
67%). For synthesis of 5 by transmetalation starting from 6, complex
[Co2(NS,NS)2] 5 was synthesized from complex [Ni2(NS,NS)2] 6 (50
mg, 0.06 mmol), dissolved in DMF (20 mL) by dropwise addition of
cobalt(II)acetate (28 mg, 0.16 mmol), dissolved in MeOH (10 mL).
After the reaction mixture stirred at ambient temperature for 48 h, the
solvent was removed in vacuo, and a MALDI mass spectrum of the
solid was recorded, which showed an uncharacteristic isotopic pattern,
indicating a mixture of complex [Ni2(NS,NS)2] 6 and complex
[Co2(NS,NS)2] 5. Recrystallization (DMF/n-hexane, 2:1, v:v) gave
crystals of complex [Co2(NS,NS)2] 5 which were suitable for X-ray
diffraction analysis. The mass spectrum of the recrystallization product
confirmed the presence 5 since it showed the same isotope pattern as
an authentic sample of 5 which is different from that of 6 although
both 5 and 6 have the same molecular weight of m/z = 810. NMR data
could not be obtained due to the poor solubility of the compound in
common deuterated solvents. MS (MALDI TOF, DCTB): m/z = 810
[5]+. IR (KBr, cm−1): ν = 1670, 1577, 1527, 1481, 1420, 1221, 799,
718. UV−vis (DMF, nm): νmax = 422.
Complex [Ni2(NS,NS)2] 6 by Transmetalation from 3.
Complex [Zn2(NS,NS)2] 3 (49 mg, 0.06 mmol) was dissolved in
DMF (20 mL), and nickel(II) acetate tetrahydrate (37 mg, 0.15
mmol) dissolved in MeOH (10 mL) was added dropwise. After the
reaction mixture stirred at ambient temperature for 12 h, n-hexane (20
mL) was added to precipitate the dark brown complex [Ni2(NS/NS)2]
6. The dark brown solid was isolated by filtration and dried in vacuo.
Yield: 32 mg (0.04 mmol, 67%). Complex [Ni(NS,NS)2] 6 was also
formed by the rearrangement reaction starting with complex
[Ni(NS,NOH)2] 9. After completion of the rearrangement (20
days), complex [Ni2(NS/NS)2] 6 was removed from the reaction
mixture by filtration. Recrystallization (DMF/n-hexane, 4:1, v:v) gave
crystals which were suitable for an X-ray diffraction analysis. The
crystal parameters and MS data of 6 obtained by transmetalation from
3 or by rearrangement of 9 are identical. NMR data could not be
obtained due to the poor solubility of the compound in common
deuterated solvents. MS (MALDI TOF, DCTB): m/z = 810 [6]+. IR
(KBr, cm−1): ν = 1588, 1522, 1457, 1217, 1076, 1021, 745, 685. UV−
vis (DMF, nm): νmax = 462, 308.
= 6.8 Hz, 2H, ArH), 3.60 (s, 4H, NH2). 13C NMR (100.6 MHz,
CDCl3, 300 K): δ = 161.7 (NCH), 153.3, 145.8, 139.8, 137.3, 134.4,
132.4, 130.2, 128.1, 123.6, 116.1, 114.2, 113.2 (ArC). MS (MALDI
TOF, DCTB): m/z = 512 [8]+. Anal. Found: C 60.78, H 4.53, N
11.13. Calcd: C 60.83, H 4.32, N 10.92. UV−vis (DMF, nm): νmax
273.
=
Complex [Ni(NS,NOH)2] 9. The complex was synthesized from
[Ni(NS,NH2)2] 8 (616 mg, 1.20 mmol) dissolved in MeOH (20 mL)
by dropwise addition of a solution of salicylaldehyde (0.3 mL, 344 mg,
2.82 mmol) in MeOH (20 mL). The reaction mixture was stirred at
ambient temperature for 12 h and subsequently filtered. The solid
residue was extracted with CH2Cl2 (20 mL), and after removal of the
solvent a brown solid was obtained. Yield: 648 mg (0.90 mmol, 75%).
1H NMR (400.1 MHz, CDCl3, 300 K): δ = 12.92 (s, 2H, OH), 9.86 (s,
2H, NiNCH), 8.44 (s, 2H, NCH), 7.96 (s, 2H, ArH), 7.61
3
3
(d, J(H,H) = 8.0 Hz, 2H, ArH), 7.47 (d, J(H,H) = 7.8 Hz, 2H,
ArH), 7.39−7.31 (m, 4H, ArH), 7.29−7.22 (m, 4H, ArH),
3
3
7.11 (d, J(H,H) = 8.0 Hz, 4H, ArH), 6.96 (d, J(H,H) = 8.4 Hz,
2H, ArH), 6.88 (t, 3J(H,H) = 7.6 Hz, 2H, ArH), 6.72 (t, 3J(H,H)
= 7.6 Hz, 2H, Ar−H). 13C NMR (100.6 MHz, CDCl3, 300 K): δ =
163.1 (NC), 161.6 (NiNC), 161.1 (ArCOH), 153.4,
147.3, 138.8, 138.5, 134.3, 133.6, 132.8, 132.5, 130.5, 128.4, 124.4,
124.1, 121.9, 119.1, 118.8, 118.4, 117.1 (ArC). MS (MALDI TOF,
DCTB): m/z = 720 [9]+. Anal. Found: C 66.18, H 4.15, N 7.58.
Calcd: C 66.58, H 4.19, N 7.77. UV−vis (DMF, nm): νmax = 271.
Compound 10. Compound 10 was formed by the rearrangement
reaction proceeding from complex [Ni(NS/NOH)2] 9. After complete
rearrangement, complex [Ni2(NS/NS)2] 6 could be removed by
filtration. Removal of the solvent from the filtered solution gave
1
compound 10 as a yellow solid. H NMR (400.1 MHz, CDCl3, 300
K): δ = 13.08 (s, 2H, OH), 8.68 (s, 2H, NCH), 7.49−7.45 (m, 1H,
ArH), 7.42−7.38 (m, 4H, ArH), 7.23−7.21 (m, 1H, ArH),
7.19 (s, 2H, ArH), 7.07−7.02 (m, 2H, ArH), 6.99−6.94 (m, 2H,
ArH). 13C NMR (100.6 MHz, CDCl3, 300 K): δ = 163.3 (NCH),
161.2 (ArCOH), 149.7, 133.4, 132.5, 130.3, 119.6, 119.2, 119.1,
117.3, 113.9 (ArC). IR (KBr, cm−1): νmax = 3056 (OH), 1622, 1591,
1569, 1496, 1461, 1279, 1156, 1031, 818, 738. MS (MALDI TOF,
DCTB): m/z = 317 [10 + H]+.
X-ray Data Collection and Structure Determination. X-ray
diffraction data were collected with a Bruker AXS APEX (Mo Kα
radiation) or an AXS SMART (Cu Kα radiation) diffractometer
equipped with a rotation anode at 153(2) K using graphite
monochromated radiation. Diffraction data were collected over the
full sphere and were corrected for absorption. The data reduction was
performed with the Bruker SMART26 program package.16 Structure
solutions were found with the SHELXS-97 package17 using the heavy-
atom method and were refined with SHELXL-9717 against all F2.
Crystal Data for 3·2DMF. Formula C46H42N6O2S4Zn2, M =
969.84, yellow block, 0.17 × 0.16 × 0.16 mm3, a = 10.2801(3) Å, b =
15.3096(4) Å, c = 14.2761(4) Å, β = 101.907(2)°, V = 2198.49(11)
Å3, monoclinic, space group P21/c, Z = 2, ρcalcd = 1.465 g cm−3, Cu Kα
radiation (λ = 1.541 78 Å), μ = 3.481 mm−1, 12 477 intensities
measured in the range 8.6° ≤ 2θ ≤ 141.9°, 4039 independent
intensities (Rint = 0.0465), 3493 observed intensities [I ≥ 2σ(I)],
empirical absorption correction (0.589 ≤ T ≤ 0.606), refinement of
273 parameters against |F2| of all independent intensities with
anisotropic thermal parameters for all non-hydrogen atoms and
hydrogen atoms on calculated positions, R = 0.0384, wR = 0.1065, Rall
= 0.0432, wRall = 0.1098.
Crystal Data for 4·2CHCl3. Formula C42H30N4Cl6Pd2S4, M =
1144.44, red prism, 0.17 × 0.07 × 0.06 mm3, a = 9.8549(4) Å, b =
10.5969(4) Å, c = 22.2206(8) Å, β = 94.6070(10)°, V = 2104.84(14)
Å3, monoclinic, space group P21/c, Z = 2, ρcalcd = 1.806 g cm−3, Mo Kα
radiation (λ = 0.710 73 Å), μ = 1.472 mm−1, 24 816 intensities
measured in the range 4.0° ≤ 2θ ≤ 61.0°, 6408 independent intensities
(Rint = 0.0258), 5525 observed intensities [I ≥ 2σ(I)], empirical
absorption correction (0.788 ≤ T ≤ 0.917), refinement of 262
parameters against |F2| of all independent intensities with anisotropic
thermal parameters for all non-hydrogen atoms and hydrogen atoms
Complex [Ni(OS)2] 7. 2-Mercaptobenzaldehyde 1 (952 mg, 6.90
mmol) was dissolved in methanol (20 mL) and mixed with a solution
of nickel(II)acetate tetrahydrate (868 mg, 3.46 mmol) in methanol
(20 mL). After the reaction mixture was stirred for 6 h at ambient
temperature, a brown solid was isolated by filtration. The precipitate
was extracted with CH2Cl2 (20 mL). Removal of the solvent in vacuo
1
gave a dark brown solid. Yield: 866 mg (2.60 mmol, 75%). H NMR
(400.1 MHz, CDCl3, 300 K): δ = 8.98 (s, 2H, OCH), 7.62 (d,
3J(H,H) = 8.2 Hz, 2H, ArH), 7.55 (d, 3J(H,H) = 7.9 Hz, 2H, Ar
H), 7.26−7.24 (m, 2H, ArH), 7.04 (t, 3J(H,H) = 7.5 Hz, 2H, Ar
H). 13C NMR (100.6 MHz, CDCl3, 300 K): δ = 189.8 (OCH),
151.7, 137.8, 133.2, 130.7, 130.6, 122.6 (ArC). MS (MALDI TOF,
DCTB): m/z = 332 [7]+. UV−vis (DMF, nm): νmax = 439, 308, 270.
Complex [Ni(NS,NH2)2] 8. Complex [Ni(OS)2] 7 (500 mg, 1.50
mmol) was dissolved in THF (20 mL), and MgSO4 (1.0 g) was added.
A solution of m-phenylenediamine (389 mg, 3.60 mmol) in THF (20
mL) was added dropwise, and the reaction mixture was stirred at
ambient temperature for 24 h. The MgSO4 was separated by filtration,
and the solvent was removed in vacuo. Column chromatography of the
residue (SiO2, CH2Cl2/MeOH = 20:1, v:v) gave 8 as a black solid.
Yield: 614 mg (1.20 mmol, 80%). 1H NMR (400.1 MHz, CDCl3, 300
3
K): δ = 9.43 (s, 2H, NCH), 7.62 (d, J(H,H) = 8.2 Hz, 2H, Ar
H), 7.26−7.21 (m, 4H, ArH), 7.18 (s, 2H, ArH), 7.04−6.99 (m,
4H, ArH), 6.83 (t, 3J(H,H) = 7.4 Hz, 2H, ArH), 6.45 (d, 3J(H,H)
F
Inorg. Chem. XXXX, XXX, XXX−XXX