Table 1 Analytical and spectroscopic data for [WO2Ln] (n = 1–7) and [MoO2Ln] (n = 2–4)
Analysisa (%)
Compound
Yield (%)
48
C
H
N
Spectroscopic datab
1H NMR: δ 8.95 (d, J = 5.4, 1 H, py), 7.79 (dt, J = 1.3, 7.7, 1 H, py), 7.40 (t, J = 6.5, 1 H, py), 7.19 (d,
[WO2L1]
44.29
(44.97)
3.21
5.07
(3.40) (5.24) J = 7.5, 2 H, aryl), 7.09–7.04 (m, 3 H, aryl and py), 6.77 (t, J = 7.5, 2 H, aryl), 6.52 (d, J = 8.1, 2 H,
aryl), 4.75 (d, J = 13.5, 2 H, C6H4CH2), 4.09–4.05 (m, 4 H, C6H4CH2 and C5H4CH2)
13C-{1H} NMR: δ 160.7, 156.2, 150.4, 140.9, 129.7, 129.4, 124.3, 123.2, 123.1, 120.8, 118.3, 61.6, 58.6
IR: ν(WO2) 937s, 907s
MS (FAB): a cluster peaking at m/z 535 (100%), [M ϩ H]ϩ
[WO2L2]
[WO2L3]
83
57
1H NMR: δ 9.00 (d, J = 5.1, 1 H, py), 8.28 (d, J = 3.0, 2 H, aryl), 8.00 (dd, J = 3.0, 9.0, 2 H, aryl), 7.88
(dt, J = 1.5, 7.8, 1 H, py), 7.49 (t, J = 6.0, 1 H, py), 7.19 (d, J = 7.8, 1 H, py), 6.78 (d, J = 9.0, 2 H,
aryl), 4.83 (d, J = 14.4, 2 H, C6H3CH2), 4.33 (d, J = 14.4, 2 H, C6H3CH2), 4.24 (s, 2 H, C5H4CH2)
13C-{1H} NMR: δ 166.2, 156.2, 150.7, 141.8, 140.7, 126.2, 125.5, 125.0, 124.1, 123.6, 119.5, 60.7, 58.7
IR: ν(WO2) 949s, 914s; ν(NO2) 1510s, 1338s
HRMS (LSI):a m/z 625.0544 (625.0535)
41.11
(41.47)
2.84
7.05
1H NMR: δ 8.97 (d, J = 5.1, 1 H, py), 8.21 (d, J = 3.0, 1 H, aryl), 7.96 (dd, J = 3.0, 9.0, 1 H, aryl), 7.84
(2.96) (7.25) (dt, J = 1.5, 7.8, 1 H, py), 7.45 (t, J = 6.3, 1 H, py), 7.25 (dd, J = 1.2, 7.5, 1 H, py), 7.15–7.08 (m, 2 H,
aryl), 6.82 (dt, J = 0.9, 7.5, 1 H, aryl), 6.71 (d, J = 9.0, 1 H, aryl), 6.58 (d, J = 7.5, 1 H, aryl), 4.84 (d,
J = 13.8, 1 H, aryl CH2), 4.75 (d, J = 13.8, 1 H, aryl CH2), 4.27 (d, J = 14.1, 1 H, aryl CH2), 4.23–4.09
(m, 3 H, aryl CH2 and C5H4CH2)
13C-{1H} NMR: δ 166.8, 160.4, 156.2, 150.5, 141.3, 140.3, 129.9, 129.6, 126.1, 125.5, 124.7, 124.3,
123.4, 122.8, 121.5, 119.4, 118.4, 61.7, 60.7, 58.6
IR: ν(WO2) 944s, 908s; ν(NO2) 1512s, 1339s
MS (FAB): a cluster peaking at m/z 590 (69%), [M ϩ H]ϩ
[WO2L4]
67
1H NMR (CDCl3): δ 9.23 (d, J = 4.5, 1 H, py), 8.07 (d, J = 2.7, 1 H, aryl), 7.97 (dd, J = 2.7, 9.0, 1 H,
aryl), 7.64 (dt, J = 1.4, 7.7, 1 H, py), 7.30 (t, J = 6.1, 1 H, py), 7.22 (d, J = 2.2, 1 H, aryl), 6.99
(d, J = 2.2, 1 H, aryl), 6.90 (d, J = 7.7, 1 H, py), 6.71 (d, J = 9.0, 1 H, aryl), 5.19–5.09 (m, 2 H, aryl),
4.27 (d, J = 16.5, 1 H, aryl CH2), 4.05–3.91 (m, 3 H, aryl CH2 and C5H4CH2), 1.28 (s, 9 H, But), 1.25
(s, 9 H, But)
13C-{1H} NMR (CDCl3): δ 166.8, 157.0, 155.5, 151.8, 143.9, 140.5, 140.3, 138.7, 125.9, 125.4, 124.6,
124.1, 124.0, 123.0, 121.9, 121.1, 119.8, 63.9, 62.4, 59.3, 34.9, 34.3, 31.5, 29.9
IR: ν(WO2) 946s, 911s; ν(NO2) 1517s, 1338s
MS (FAB): a cluster peaking at m/z 691 (100%), [M ϩ H]ϩ
HRMS (LSI):a m/z 692.1769 (692.1936)
[WO2L5]
[WO2L6]
[WO2L7]
80
65
43
41.61
(42.04)
4.25
5.34
1H NMR: δ 7.30 (t, J = 8.1, 2 H, aryl), 7.23 (d, J = 7.5, 2 H, aryl), 6.90 (t, J = 7.5, 2 H, aryl), 6.79 (d,
(4.31) (5.45) J = 8.1, 2 H, aryl), 4.46 (d, J = 14.4, 2 H, C6H4CH2), 4.08 (d, J = 14.4, 2 H, C6H4CH2), 2.76–2.74 (m,
2 H, CH2CH2), 2.57 (s, 6 H, CH3), 2.52–2.50 (m, 2 H, CH2CH2)
13C-{1H} NMR: δ 159.4, 129.9, 129.8, 123.8, 121.2, 118.2, 61.6, 57.1, 52.0, 49.7
IR: ν(WO2) 938s, 912s
MS (FAB): a cluster peaking at m/z 515 (66%), [M ϩ H]ϩ
41.82
(42.04)
4.31
5.34
1H NMR: δ 7.28 (t, J = 8.1, 2 H, aryl), 7.15 (d, J = 7.5, 2 H, aryl), 6.90 (t, J = 7.5, 2 H, aryl), 6.79 (d,
(4.31) (5.45) J = 8.1, 2 H, aryl), 4.73 (d, J = 14.4, 2 H, C6H4CH2), 3.83 (d, J = 14.4, 2 H, C6H4CH2), 2.82 (d, J = 9.6,
2 H, CH2CH2), 2.63 (s, 6 H, CH3), 2.43 (d, J = 9.6, 2 H, CH2CH2)
13C-{1H} NMR: δ 157.5, 130.0, 129.5, 122.9, 121.2, 119.0, 63.5, 51.9, 47.6
IR: ν(WO2) 942m, 907s
MS (FAB): a cluster peaking at m/z 515 (100%), [M ϩ H]ϩ
1H NMR: δ 8.21–8.18 (m, 4 H, aryl), 7.03 (d, J = 7.8, 2 H, aryl), 4.74 (d, J = 14.7, 2 H, C6H3CH2),
4.15 (d, J = 14.7, 2 H, C6H3CH2), 2.84 (d, J = 9.6, 2 H, CH2CH2), 2.67 (s, 6 H, CH3), 2.54 (d, J = 9.6,
2 H, CH2CH2)
13C-{1H} NMR: δ 163.1, 141.0, 126.4, 125.7, 124.1, 120.2, 62.5, 52.3, 47.8
IR: ν(WO2) 934s, 910s; ν(NO2) 1518s, 1343s
MS (FAB): a cluster peaking at m/z 605 (33%), [M ϩ H]ϩ
HRMS (LSI):a m/z 605.0846 (605.0848)
[MoO2L2]
[MoO2L3]
90
87
44.64
(44.79)
2.97
10.54 1H NMR: δ 9.01 (d, J = 5.1, 1 H, py), 8.25 (d, J = 3.0, 2 H, aryl), 7.95 (dd, J = 3.0, 9.0, 2 H, aryl), 7.86
(3.01) (10.45) (t, J = 7.8, 1 H, py), 7.48 (t, J = 6.4, 1 H, py), 7.19 (d, J = 7.8, 1 H, py), 6.74 (d, J = 9.0, 2 H, aryl),
4.75 (d, J = 14.4, 2 H, C6H3CH2), 4.26 (d, J = 14.4, 2 H, C6H3CH2), 4.11 (s, 2 H, C5H4CH2)
13C-{1H} NMR: δ 168.1, 155.2, 150.4, 141.4, 140.4, 126.3, 125.4, 124.9, 124.1, 123.7, 118.8, 60.6, 58.5
IR: ν(MoO2) 918s (br); ν(NO2) 1511s, 1339s
HRMS (LSI):a m/z 539.0064 (539.0106)
48.50
(48.89)
3.29
8.35
1H NMR: δ 8.99 (d, J = 4.8, 1 H, py), 8.20 (d, J = 2.7, 1 H, aryl), 7.92 (dd, J = 2.7, 9.0, 1 H, aryl), 7.83
(3.49) (8.55) (dt, J = 1.5, 7.5, 1 H, py), 7.45 (t, J = 6.3, 1 H, py), 7.25 (dd, J = 1.5, 7.5, 1 H, py), 7.15 (d, J = 7.8,
1 H, aryl), 7.08 (dt, J = 1.5, 7.8, 1 H, aryl), 6.83 (dt, J = 0.9, 7.2, 1 H, aryl), 6.67 (d, J = 9.0, 1 H,
aryl), 6.58 (d, J = 7.8, 1 H, aryl), 4.76 (d, J = 14.1, 1 H, aryl CH2), 4.62 (d, J = 14.1, 1 H, aryl CH2),
4.17 (d, J = 14.1, 1 H, aryl CH2), 4.08 (d, J = 14.1, 1 H, aryl CH2), 4.04 (s, 2 H, C5H4CH2)
13C-{1H} NMR: δ 168.8, 162.4, 155.3, 150.3, 141.0, 139.8, 130.0, 129.3, 126.2, 125.5, 124.6, 124.3,
123.6, 122.8, 121.4, 118.8, 117.4, 61.4, 60.5, 58.5
IR: ν(MoO2) 944s, 908s; ν(NO2) 1512s, 1339s
MS (FAB): a cluster peaking at m/z 494 (17%), [M ϩ H]ϩ
[MoO2L4]
84
1H NMR (CDCl3): δ 9.20 (d, J = 4.9, 1 H, py), 8.06 (d, J = 2.7, 1 H, aryl), 7.94 (dd, J = 2.7, 9.0, 1 H,
aryl), 7.63 (dt, J = 1.2, 7.8, 1 H, py), 7.30 (t, J = 6.4, 1 H, py), 7.19 (d, J = 2.3, 1 H, aryl), 6.99
(d, J = 2.3, 1 H, aryl), 6.89 (d, J = 7.8, 1 H, py), 6.68 (d, J = 9.0, 1 H, aryl), 5.01–4.91 (m, 2 H, aryl
CH2), 4.13 (d, J = 16.2, 1 H, aryl CH2), 3.92–3.82 (m, 3 H, aryl CH2 and C5H4CH2), 1.28 (s, 9 H, But),
1.26 (s, 9 H, But)
13C-{1H} NMR (CDCl3): δ 168.9, 159.2, 154.7, 151.3, 143.7, 139.9, 137.5, 125.7, 125.5, 124.2, 123.8,
122.9, 122.1, 121.3, 119.2, 63.5, 62.1, 59.1, 35.0, 34.3, 31.5, 29.9
IR: ν(MoO2) 910s (br); ν(NO2) 1510s, 1333s
HRMS (LSI):a m/z 606.1475 (606.1507)
a Calculated values given in parentheses. b The NMR spectra were obtained at r.t. in CD3SOCD3 unless otherwise stated; data given as chemical shift
(δ), multiplicity (s = singlet, d = doublet, t = triplet, m = multiplet), coupling constant (Hz), relative intensity and assignment. The IR spectra (cmϪ1
)
were recorded as KBr pellets. For high resolution mass spectra the values of m/z quoted are based on the most abundant isotope of each element in
[M ϩ H]ϩ. The bands show the predicted isotopic patterns.
3060
J. Chem. Soc., Dalton Trans., 1998, 3057–3064