8
40
Bull. Chem. Soc. Jpn. Vol. 86, No. 7 (2013)
Oxygen/Sulfur-Bridged Incomplete Cubane-Type Clusters
+
Scheme 1. Preparation scheme of [M3OnS4¹n(Tpe)3] (M = Mo and W, n = 0, 1).
J = 9.7 Hz), 5.38 (d, 3H, J = 9.7 Hz), 6.37 (t, 3H, J = 2.5 Hz),
.83 (t, 3H, J = 2.5 Hz), 6.89 (t, 3H, J = 2.3 Hz), 7.49 (d, 3H,
J = 2.8 Hz), 7.60 (d, 3H, J = 2.5 Hz), 8.22 (d, 3H, J = 2.1 Hz),
.35 (d, 3H, J = 2.5 Hz), 8.44 (d, 3H, J = 2.1 Hz), 8.66 (d, 3H,
was recrystallized from dichloromethane (100 mL) to obtain
a crystalline product of [W S (Tpe) ]PF ¢4CH Cl ([7]PF ¢
6
3
4
3
6
2
2
6
4CH Cl ). Yield: 30 mg, (10%). Anal. Calcd for [7]PF ¢
2
2
6
8
0.5CH Cl (C H N ClO S PF W ): C, 25.20; H, 2.15; N,
2 2 34 34 18 3 4 6 3
1
J = 2.1 Hz).
15.79%. Found: C, 25.28; H, 1.93; N, 15.78%. H NMR
The following compounds (except 11) were prepared by a
similar procedure to that used in the preparation of complex 5.
(CD CN, 298 K): ¤ 5.12 (d, 3H, J = 9.8 Hz), 5.51 (d, 3H,
3
J = 9.8 Hz), 6.41 (t, 3H, J = 2.5 Hz), 6.84 (t, 3H, J = 2.5 Hz),
6.89 (t, 3H, J = 2.3 Hz), 7.44 (d, 3H, J = 2.4 Hz), 7.58 (d, 3H,
J = 2.8 Hz), 8.21 (d, 3H, J = 1.9 Hz), 8.33 (d, 3H, J = 2.5 Hz),
8.75 (t, 6H, J = 3.3 Hz).
[
Mo OS (Tpe) ]PF ¢4CH Cl ([6]PF ¢4CH Cl ). KPF6
3 3 3 6 2 2 6 2 2
(
155 mg, 0.84 mmol) was added to a green solution of
4+
¹3
[Mo OS (H O) ] (2) (in 0.1 M HCl, 6.6 © 10 M per trimer,
3 3 2 9
5
0 mL). A dichloromethane solution (250 mL) containing HTpe
[W OS (Tpe) ]PF ¢2.5CH Cl ([8]PF ¢2.5CH Cl ). KPF6
3
3
3
6
2
2
6
2
2
(
1209 mg, 4.95 mmol) was added to the solution and stirred
(110 mg, 0.6 mmol) was added to a purple solution of [W OS -
3 3
4+
10
¹3
for two days. The organic layer was separated and solvent
was removed under vacuum. The green residue was washed by
Et O (200 mL) to remove unreacted HTpe. The green powder
was recrystallized from dichloromethane to obtain a crystalline
product of [Mo OS (Tpe) ]PF ¢4CH Cl ([6]PF ¢4CH Cl ).
(H2O)9] (4) (in 0.1 M HCl, 8.0 © 10 M per trimer, 25
mL). A dichloromethane solution (150 mL) containing HTpe
(733 mg, 3.0 mmol) was added to the solution and stirred for
two days. The organic layer was separated and solvent was
removed under vacuum. The purple residue was washed by
2
3
3
3
6
2
2
6
2
2
Yield: 290 mg, (69%). Anal. Calcd for [6]PF (C H N O -
Et O (200 mL) to remove unreacted HTpe. The purple powder
2
6
33 33 18
4
Mo S PF ): C, 31.09; H, 2.61; N, 19.78%. Found: C, 31.17;
was recrystallized from dichloromethane (100 mL) to obtain a
crystalline product of [W OS (Tpe) ]PF ¢2.5CH Cl ([8]PF ¢
3
3
6
1
H, 2.60; N, 19.57%. H NMR (CD Cl , 298 K): ¤ 5.15 (d, 1H,
2
2
3
3
3
6
2
2
6
J = 9.6 Hz), 5.32 (d, 1H, J = 9.6 Hz), 5.32 (d, 1H, J = 9.6 Hz),
.40 (d, 1H, J = 9.6 Hz), 5.45 (d, 1H, J = 9.6 Hz), 5.50 (d, 1H,
J = 9.6 Hz), 6.31 (t, 1H, J = 2.5 Hz), 6.32 (t, 1H, J = 2.5 Hz),
.38 (t, 1H, J = 2.5 Hz), 6.67 (t, 1H, J = 2.5 Hz), 6.70 (t, 1H,
J = 2.5 Hz), 6.75 (t, 1H, J = 2.5 Hz), 6.82 (t, 1H, J = 2.5 Hz),
.83 (t, 1H, J = 2.5 Hz), 6.84 (t, 1H, J = 2.5 Hz), 7.35 (d, 1H,
J = 2.5 Hz), 7.42 (d, 1H, J = 3.0 Hz), 7.45 (d, 1H, J = 3.0 Hz),
.47 (d, 1H, J = 3.0 Hz), 7.48 (d, 1H, J = 3.0 Hz), 7.55 (d, 1H,
J = 2.7 Hz), 8.07 (br s, 1H), 8.10 (d, 1H, J = 2.1 Hz), 8.12 (d,
H J = 2.2 Hz), 8.14 (d, 1H, J = 2.4 Hz), 8.15 (d, 1H, J = 2.4
Hz), 8.17 (d, 1H, J = 2.0 Hz), 8.18 (d, 1H, J = 2.0 Hz), 8.18 (d,
2.5CH2Cl2). Yield: 132 mg, (43%). Anal. Calcd for [8]PF6
(C H N O W S PF ): C, 25.76; H, 2.16; N, 16.39%. Found:
5
3
3
33 18
4
3
3
6
1
C, 25.75; H, 1.90; N, 16.13%. H NMR (CD Cl , 298 K):
2
2
6
¤ 5.09 (d, 1H, J = 9.6 Hz), 5.22 (d, 1H, J = 9.6 Hz), 5.29
(d, 1H, J = 9.6 Hz), 5.41 (d, 1H, J = 9.6 Hz), 5.53 (d, 1H, J =
9.6 Hz), 5.60 (d, 1H, J = 9.6 Hz), 6.34 (t, 1H, J = 2.5 Hz), 6.35
(t, 1H, J = 2.5 Hz), 6.41 (t, 1H, J = 2.5 Hz), 6.68 (t, 1H, J =
2.5 Hz), 6.71 (t, 1H, J = 2.5 Hz), 6.75 (t, 1H, J = 2.5 Hz), 6.82
(t, 1H, J = 2.0 Hz), 6.83 (t, 1H, J = 2.0 Hz), 6.84 (t, 1H, J =
2.0 Hz), 7.30 (d, 1H, J = 2.8 Hz), 7.38 (d, 1H, J = 2.8 Hz),
7.41 (d, 1H, J = 2.8 Hz), 7.42 (d, 1H, J = 2.8 Hz), 7.46 (d, 1H,
J = 2.8 Hz), 7.53 (d, 1H, J = 2.8 Hz), 8.10 (br s, 1H), 8.12 (d,
1H, J = 2.8 Hz), 8.13 (br s, 1H), 8.15 (br s, 1H), 8.16 (d, 1H,
J = 2.8 Hz), 8.16 (d, 1H, J = 2.8 Hz), 8.18 (d, 1H, J = 2.1 Hz),
8.18 (d, 1H, J = 2.1 Hz), 8.36 (d, 1H, J = 2.1 Hz), 8.59 (d, 1H,
J = 2.0 Hz), 8.89 (d, 1H, J = 2.0 Hz), 9.10 (br s, 1H).
6
7
1
1
2
H, J = 2.0 Hz), 8.20 (d, 1H, J = 3.0 Hz), 8.32 (d, 1H, J =
.1 Hz), 8.73 (d, 1H, J = 2.1 Hz), 8.84 (br s, 1H).
[
W S (Tpe) ]PF ¢4CH Cl ([7]PF ¢4CH Cl ). KPF (105
3 4 3 6 2 2 6 2 2 6
mg, 0.57 mmol) was added into a purple solution of [W S -
3
4
4+
9
¹3
(
H O) ] (3) (in 0.1 M HCl, 7.6 © 10 M per trimer, 25
2 9
mL). A dichloromethane solution (150 mL) containing HTpe
696 mg, 2.85 mmol) was added to the solution and stirred
two days. The organic layer was separated and solvent was
removed under vacuum. The purple residue was washed by
[Mo3PdS4Cl(Tpe)3]¢4.5CH2Cl2 ([11]¢4.5CH2Cl2).
This
(
compound was prepared under an N2 atmosphere. Cluster
[5]PF ¢3CH Cl (100 mg, 0.078 mmol) was dissolved in
6
2
2
acetonitrile (40 mL). [Pd (dba) ] (71 mg, 0.078 mmol) and bis-
2
3
Et O (200 mL) to remove unreacted HTpe. The purple powder
2
(triphenylphosphoranylidene)ammonium chloride (=PPNCl,