Inorganic Chemistry
ARTICLE
1,4-Bis[(3,5-dipyridin-2-yl-1H-pyrazol-4-yl)methyl]benzene [3a; (Hbpp)2-
p-xyl]. Yield: 108 mg (60%). Elem anal. Calcd for (C34H26N8): C, 74.71;
H, 4.79; N, 20.50. Found: C, 73.76; H, 4.70; N, 19.89. 1H NMR (400 MHz,
D2O/CF3COOD): δ 8.73 (ddd, 4 H, 3J14-13 = 5.94 Hz, 4J14-12 = 1.57 Hz,
5J14-11 = 0.56 Hz, H14), 8.42 (td, 4 H, 3J12-11,13 = 8.05 Hz, 4J12-14 = 1.57
H, 3J14-13 = 5.65 Hz, 4J14-12 = 1.50 Hz, 5J14-11 = 0.78 Hz, H14), 7.45 (t, 2
H, 3J3-2,4 = 7.56 Hz, 3H, 5H), 7.34 (t, 1 H, 3J4-3,5 = 7.56 Hz, 4H), 6.77
(ddd, 2 H, 3J13-12 = 7.49 Hz, 3J13-14 = 5.65 Hz, 4J13-11 = 1.40 Hz, H13),
5.24 (s, 2H, H14) . 13C{1H} NMR (100.6 MHz, acetone-d6): δ 160.214
(C21), 159.787 (C10), 159.459 (C22), 154.792 (C14), 154.156 (C17),
147.480 (C9), 140.236 (C1), 138.036 (C19), 137.582 (C12), 134.912
(C24), 129.934 (C3), 129.115 (C2), 128.216 (C18), 127.565 (C4),
124.507 (C20), 123.344 (C23), 122.834 (C13), 121.284 (C11), 120.987
(C8), 30.78 (C7). ESI-MS (MeOH): m/z 1161 ([M - PF6-]þ). UV-vis
(CH2Cl2) [λmax, nm (ε, M-1 cm-1)]: 279 (59 516), 317 (56 452), 387
(25 226), 477 (16 581), 503 (15 032).
Hz, 12H), 7.93 (ddd, 4 H, 3J13-12 = 8.05 Hz, 3J13-14 = 5.94 Hz, 4J13-11
=
1.20 Hz, H13), 7.86 (ddd, 4 H, 3J11-12 = 8.05 Hz, 4J11-13 = 1.20 Hz, 5J11-14
= 0.56 Hz, H11), 6.74 (s, 4 H, H2, H3, H5, H6), 4.10 (s, 4 H, H7). 13C{1H}
NMR (100.6 MHz, D2O/CF3COOD): δ 147.77 (C12), 142.90 (C14),
142.59 (C10), 139.20 (C9), 136.69 (C1, C4), 128.91 (C2, C3, C5, C6),
127.21 (C13), 127.12 (C11), 121.59 (C8), 28.30 (C7). ESI-MS (MeOH):
m/z 546.6, 547.6 ([M þ Hþ]þ).
{[RuII2(trpy)2(μ-Cl)]2(μ-(bpp)2-p-xyl)}(PF6)4 [7(PF6)4]. Yield: 120 mg
(44%). 1H NMR (250 MHz, acetone-d6): δ 8.66 (d, 8 H,
1,3-Bis[(3,5-dipyridin-2-yl-1H-pyrazol-4-yl)methyl]benzene [3b; (Hbpp)2-
m-xyl]. Yield: 56 mg (31%). Elem anal. Calcd for (C34H26N8): C, 74.7; H, 4.8;
3
4
3J23-24 = 8.09 Hz, H23), 8.52 (ddd, 8 H, J20-19 = 8.38 Hz, J20-18
=
=
1
N, 20.5. Found: C, 74.9; H, 4.9; N, 20.1. H NMR (360 MHz, D2O/
1.25 Hz, 5J20-17 =0.6Hz, H20), 8.35(ddd, 8H, 3J17-18 =5.53Hz, 4J17-19
CF3COOD): δ8.65 (ddd, 4 H, 3J14-13 = 5.93 Hz, 4J14-12 = 1.63 Hz, 5J14-11
=
1.33 Hz, 5J17-20 = 0.6 Hz, H17), 8.15 (t, 4 H, 3J24-23 = 8.09 Hz, H24), 8.07
(ddd, 4 H, 3J14-13 = 8.08 Hz, 4J14-12 = 1.30 Hz, 5J14-11 = 0.63 Hz, H14),
7.93 (ddd, 8 H, 3J19-20 = 8.38 Hz, 3J19-18 = 7.38 Hz, 4J19-17 = 1.37 Hz,
H19), 7.87 (s, 4 H, H2, H3, H5, H6), 7.61 (ddd, 8 H, 3J18-19 = 7.38 Hz,
3J18-17 = 5.53 Hz, 4J18-10 = 1.25 Hz, H18), 7.59 (ddd, 4 H, 3J13-14 = 8.08
0.75 Hz, H14), 8.35 (td, 4 H, 3J12-13,11 = 8.05 Hz, 4J12-14 = 1.63 Hz), 7.87
(ddd, 4 H, 3J13-12 = 8.05 Hz, 3J13-14 = 5.93 Hz, 4J13-11 = 1.27 Hz, H13), 7.75
(ddd, 4 H, 3J11-12 = 8.05 Hz, 4J11-13 = 1.27 Hz, 5J11-14 = 0.75 Hz, H11), 6.86
(t,1H,3J3-4,2 = 7.80 Hz, H3), 6.68 (d, 2 H, 3J4-3 = 7.80 Hz, H4, H2), 6.49 (s, 1
H, H6), 4.05 (s, 4 H, H7). 13C{1H} NMR (90.5 MHz, D2O/CF3COOD):
δ 148.63 (C12), 143.68 (C14), 143.31 (C10), 139.97 (C9), 139.44
(C1), 130.97 (C3), 128.94 (C6), 128.22 (C4, C2), 128.14 (C11), 128.08
(C13), 122.55 (C8), 29.38 (C7). ESI-MS (MeOH): m/z 546.6, 547.2
([M þ Hþ]þ).
Hz, 3J13-12 = 7.49 Hz, 4J13-11 = 1.45 Hz, H13), 7.46 (ddd, 4 H, 3J11-12
=
5.78 Hz, 4J11-13 = 1.45 Hz, 5J11-14 = 0.63 Hz, H11), 6.71 (ddd, 4 H12, 3J12-
13 = 7.49 Hz, 3J12-11 = 5.78 Hz, 4J12-14 = 1.30 Hz, H12), 5.25 (s, 4 H, H7) .
13C{1H} NMR (62.9 MHz, acetone-d6): δ 160.21 (C21), 159.78 (C11),
159.45 (C22), 154.77 (C11), 154.08 (C17), 147.47 (C9), 138.82 (C2,
C5), 138.03 (C19), 137.47 (C13), 134.92 (C24), 129.92 (C2, C3, C5, C6),
128.22 (C18), 124.54 (C10), 123.36 (C23), 122.82 (C12), 121.36 (C14),
121.26 (C8), 30.59 (C7). UV-vis (CH2Cl2) [λmax, nm (ε, M-1 cm-1)]:
276 (118 562), 315 (102 710), 383 (43 273), 476 (29 974), 507 (27 410).
1,2-Bis[(3,5-dipyridin-2-yl-1H-pyrazol-4-yl)methyl]benzene [3c; (Hbpp)2-
o-xyl]. Yield: 43 mg (24%). Elem anal. Calcd for (C34H26N8): C, 74.71;
H, 4.79; N, 20.50. Found: C, 73.58; H, 5.09; N, 19.25. 1H NMR (400 MHz,
D2O/CF3COOD): δ 8.72 (dd, 4H, 3J14-13 = 5.92 Hz, 4J14-12 = 1.22 Hz,
3
4
H14), 8.34 (td, 4 H, J12-13,11 = 8.02 Hz, J12-14 = 1.22 Hz, H12), 7.92
(ddd, 4 H, 3J13-12 = 8.02 Hz, 3J13-14 = 5.92 Hz, 4J13-11 = 0.95 Hz, H13), 7.64
(d, 4 H, 3J11-12 = 8.02 Hz, H11), 6.92 (dd, 2 H, 3J2-3 = 5.78 Hz, 4J2-4 = 3.58
Hz, H2, H5), 6.77 (dd, 2 H, 3J3-4 = 5.78 Hz, 4J3-5 = 3.58 Hz, H3, H4), 4.06
(s, 4 H, H7). 13C{1H} NMR (100.6 MHz, D2O/CF3COOD): δ 148.82
(C12), 144.28 (C14), 143.70 (C10), 140.52 (C9), 136.57 (C8), 130.26 (C3,
C4), 130.03 (C2, C5), 128.62 (C13), 127.83 (C11), 121.63 (C1, C6), 28.02
(C7). ESI-MS (MeOH): m/z 546.6, 547.2 ([M þ Hþ]þ).
ESI-MS (MeOH): m/z 1121.5 ([M - 2PF6 ]
- 2þ).
{[RuII (trpy)2(μ-Cl)]2(μ-(bpp)2-m-xyl)}(PF6)4 [8(PF6)4]. Yield:
2
92 mg (34%). 1H NMR (400 MHz, acetone-d6): δ 8.62 (d, 8 H, 3J23-24
= 8.10 Hz, H23), 8.48 (d, 8 H, 3J20-19 = 7.80 Hz, H20), 8.37 (dd, 8 H,
3J17-18 = 5.46 Hz, 4J17-19 = 1.10 Hz, H17), 8.23 (s, 1 H, H6), 8.10
3
3
(t, 4 H, J24-23 = 8.10 Hz, H24), 8.04 (d, 4 H, J11-12 = 7.52 Hz,
H11), 7.89 (td, 8 H, 3J19-18,20 = 7.8 Hz, 4J19-17 = 1.10 Hz, H19), 7.64
(ddd, 8 H, 3J18-19 = 7.80 Hz, 3J18-17 = 5.46 Hz, 4J18-20 = 0.80 Hz,
H18), 7.64-7.54 (m, 3 H, H2, H3, H4), 7.46 (t, 4 H, 3J12-13,11 = 7.52
General Synthetic Procedure for Complexes 4(PF6)2, 7(PF6)4,
8(PF6)4, and 9(PF6)4. A sample of 0.214 g (0.485 mmol) of
[RuCl3(trpy)] and 61.7 mg (1.455 mmol) of LiCl was dissolved in dried
MeOH (20 mL) containing 135.5 μL (0.97 mmol) of NEt3. The mixture
was stirred at room temperature for 20 min, and then dried MeOH (6 mL)
containing bpp-bz- (0.2445 mmol) or (bpp)2-u-xyl2- (0.489 mmol) was
added. Deprotonation was performed by the addition of a stoichiometric
amount of 0.207 M MeONa. The resulting solution was heated at reflux for
4 h in the dinuclear case and overnight for the tetranuclear case and then
stirred in the presence of a 100 W tungsten lamp for 12 h. The resulting
solution was filtered, and a saturated NH4PF6 aqueous solution (1 mL) and
water (3 mL) were added. The volume was reduced on a rotary evaporator
until a precipitate appeared, and then the solution was allowed to set at low
temperature for 1 day to obtain a good precipitate. The solid was filtered on
a frit, washed with cold water (3 ꢀ 5 mL) and ether (3 ꢀ 5 mL), and dried
under vacuum. Yields and characterizations are given below.
Hz, H12), 7.45 (d, 4 H, 3J14-13 = 6.21 Hz, H14), 6.69 (ddd, 4 H, 3J13-12
=
7.52 Hz, 3J13-14 = 6.21 Hz, 4J13-11 = 1.35 Hz, H13), 5.38 (s, 4 H, H7) .
13C{1H} NMR (100.6 MHz, acetone-d6): δ 160.16 (C21), 159.80
(C10), 159.42 (C22), 154.77 (C14), 154.10 (C17), 147.48 (C8),
141.19 (C1, C4), 138.01 (C19), 137.38 (C12), 134.90 (C24), 131.09
(C2, C4, or C3), 129.62 (C6), 128.33 (C18), 127.12 (C3 or C2, C4),
124.51 (C20), 123.33 (C23), 122.77 (C13), 121.20 (C11), 121.10
(C9). UV-vis (CH2Cl2) [λmax, nm (ε, M-1 cm-1)]: 275 (121 704),
315 (99 987), 383 (41 593), 476 (29 333), 507 (26 646). ESI-MS
(MeOH): m/z 2388.3 ([M - PF6-]þ).
{[RuII2(trpy)2(μ-Cl)]2(μ-(bpp)2-o-xyl)}(PF6)4 [9(PF6)4]. Yield: 111 mg
1
3
(41%). H NMR (360 MHz, acetone-d6): δ 8.68 (d, 8 H, J23-24
=
3
8.10 Hz, H23), 8.55 (d, 8 H, J20-19 = 7.85 Hz, H20), 8.49 (dd, 8 H,
3J17-18 = 5.42 Hz, 4J17-19 = 1.40 Hz, H17), 8.16 (t, 4 H, 3J24-23 = 8.10 Hz,
H24), 7.99 (d, 4 H, 3J11-12 = 7.65 Hz, H11), 7.97 (td, 8 H, 3J19-18,20
7.85 Hz, 4J19-17 = 1.40 Hz, H19), 7.84 (dd, 2 H, 3J2-3 = 5.50 Hz, 4J2-4
=
=
{[RuII (trpy)2(μ-Cl)](μ-bpp-bz)}(PF6)2 [4(PF6)2]. Yield: 199 mg
2
3.40 Hz, H2, H5), 7.67 (ddd, 8 H, 3J18-19 = 7.85 Hz, 3J18-17 = 5.42 Hz,
4J18-20 = 1.20 Hz, H18), 7.62 (td, 4 H, 3J12-13,11 = 7.65 Hz, 4J12-14 = 1.35
(63%). Elem anal. Calcd for (C50H37N10Ru2P2F12): C, 46.0; H, 2.8; N,
10.7. Found: C, 45.9; H, 2.9; N, 10.6. 1H NMR (400 MHz, acetone-d6): δ
8.66 (d, 4 H, 3J23-24 = 8.12 Hz, H23), 8.52 (ddd, 4 H, 3J20-19 = 8.06 Hz,
4J20-18 = 1.31 Hz, 5J20-17 = 0.72 Hz, H20), 8.37 (ddd, 4 H, 3J17-18 = 5.50
Hz, 4J17-19 = 1.51 Hz, 5J17-20 = 0.72 Hz, H17), 8.15 (t, 2 H, 3J24-23 = 8.12
Hz, H24), 8.10(ddd, 2H, 3J11-12 =8.17Hz, 4J11-13 =1.4Hz, 5J11-14 =0.78
Hz, H12), 7.51 (ddd, 4 H, 3J14-13 = 5.65 Hz, 4J14-12 = 1.35 Hz, 5J14-11
=
0.50 Hz, H14), 7.38 (dd, 2 H, 3J3-2 = 5.50 Hz, 4J3-5 = 3.40 Hz, H3, H4),
6.75 (ddd, 4 H, 3J13-12 = 7.65 Hz, 3J13-14 = 5.65 Hz, 4J13-11 = 1.30 Hz,
H13), 5.76 (s, 4 H, H7). 13C{1H} NMR (90.5 MHz, acetone-d6): δ
160.22 (C21), 159.92(C10), 159.52 (C22), 154.84 (C14), 154.30 (C17),
147.97 (C8), 138.30 (C1, C6), 138.05 (C19), 137.37 (C12), 134.92
(C24), 128.57 (C2, C5), 128.52 (C3, C4), 128.35 (C18), 124.53 (C20),
123.35 (C23), 122.82 (C13), 121.38 (C11), 120.20 (C9), 28.72 (C7).
Hz, H11), 7.95 (ddd, 4 H, 3J19-20 = 8.06 Hz, 3J19-18 = 7.65 Hz, 4J19-17
=
1.51 Hz, H19), 7.72 (ddd, 2 H, 3J12-11 = 8.17 Hz, 3J12-13 = 7.49 Hz, 4J12-14
= 1.50 Hz, H12), 7.71 (d, 2 H, 3J2-3 = 7.56 Hz, H2, H6), 7.60 (ddd, 4 H,
3J18-19 = 7.65 Hz, 3J18-17 = 5.50 Hz, 4J18-10 = 1.31 Hz, H18), 7.47 (ddd, 2
2773
dx.doi.org/10.1021/ic101802y |Inorg. Chem. 2011, 50, 2771–2781