T.S. Basu Baul et al. / Journal of Organometallic Chemistry 692 (2007) 3625–3635
3629
The orange product was recrystallized from a benzene–
2.4.4. {[nOct2Sn(L3H)]2O}2 (4)
hexane mixture. Yield: 1.16 g, 92.8%. m.p.: 124–126 ꢁC. Anal.
Orange prismatic crystals of compound 4, m.p.
74–76 ꢁC, were obtained from benzene–acetonitrile (v/v
2:1) in 65.6% yield. Anal. Calc. for C120H180N8O14Sn: C,
59.24; H, 7.47; N, 4.61. Found: C, 59.30; H, 7.51; N,
4.65%. IR (KBr, cmꢁ1): 1628 m(OCO)asym, 623m(Sn–O–Sn).
For NMR: refer to Section 3.2 for specific comments.
ESI-MS: MW = 2436. Mmono = 600 = L3SnOct2-H. Posi-
tive-ion MS: m/z 601 [Mmono+H]+. MS/MS of m/z 601: m/z
583 [Mmono+HꢁH2O]+; m/z 557 [Mmono+HꢁCO2]+; m/z
+Hꢁoctane–octene]+; m/z 331 [Mmono+Hꢁoctane–octene–
CO2]+. Negative-ion MS: m/z 2453 [MꢁH+H2O]ꢁ; m/z
2435 [MꢁH]ꢁ; m/z 2311 [3*Mmono+L3+L3H]ꢁ; m/z 2055
[3*Mmono+L3]ꢁ; m/z 1711 [2*Mmono+L3+L3H]ꢁ; m/z 1491
[2*Mmono+Cl+L3H]ꢁ; m/z 1455 [2*Mmono+L3]ꢁ; m/z 1235
[2*Mmono+Cl]ꢁ; m/z 855 [Mmono+L3]ꢁ; m/z 635
[Mmono+Cl]ꢁ; m/z 255 [L3]ꢁ, 100%; m/z 211 [L3–CO2]ꢁ.
MS/MS of m/z 2435: m/z 2417 [MꢁH–H2O]ꢁ; m/z 2179
[MꢁH–L3H]ꢁ; m/z 1817 [MꢁH–MmonoꢁH2O]ꢁ; m/z 1579
[MꢁH–L3H–Mmono]ꢁ; m/z 1217 [MꢁHꢁ2*MmonoꢁH2O]ꢁ;
m/z 855 [Mmono+L3]ꢁ. MS/MS of m/z 2055: m/z 1455
[2*Mmono+L3]ꢁ; m/z 855 [Mmono+L3]ꢁ. MS/MS of m/z 855:
m/z 255 [L3]ꢁ. 119Sn Mo¨ssbauer: d = 1.37, D = 3.46,
C1 = 0.81, C2 = 0.81 mm sꢁ1, q = 2.53, C–Sn–C = 141ꢁ.
Calc. for C44H56N4O6Sn: C, 61.77; H, 6.60; N, 6.0. Found: C,
61.9; H, 6.7; N, 6.2%. IR (KBr, cmꢁ1): 1628m (OCO)asym
.
1H NMR (CDCl3, 300.13 MHz); dH: Ligand skeleton: 2.45
[s, 3H, CH3], 7.13 [d, 1H, H-3], 7.32 [d, 2H, H-20 and H-60],
7.85 [d, 2H, H-30 and H-50], 8.12 [dd, 1H, H-4], 8.64 [d, 1H,
H-6], 10.98 [s, 1H, OH]; Sn-nOct skeleton: 0.83 [m, 3H,
CH3], 1.10–2.0 [m, 14H, CH2], ppm. 13C NMR (CDCl3,
75.47 MHz); dC: Ligand skeleton: 21.5 [CH3], 112.9 [C-1],
118.3 [C-3], 122.8 [C-20 and C-60], 128.4 [C-6], 129.0 [C-4],
129.7 [C-30 and C-50], 141.2 [C-40], 145.7 [C-5], 150.8
[C-10], 163.7 [C-2], 177.5 [CO2]; Sn-nOct skeleton: 14.0
[CH3], 22.6 [gCH2], 24.5 [fCH2], 26.9 [eCH2], 28.9 [dCH2],
29.1 [cCH2], 31.7 [bCH2], 33.3 [aCH2], ppm. 119Sn NMR
(CDCl3, 111.92 MHz); dSn: ꢁ115.0 ppm. ESI-MS:
MW = 856. Mmono = 600 = L4SnOct2-H. Positive-ion MS:
m/z 601 [Mmono+H]+. MS/MS of m/z 601: m/z 583 [Mmono
+HꢁH2O]+; m/z 557 [Mmono+HꢁCO2]+; m/z 443 [Mmono
+Hꢁoctane–CO2]+; m/z 375 [Mmono+Hꢁoctane–octene]+;
m/z 331 [Mmono+Hꢁoctane–octene–CO2]+. Negative-ion
MS: m/z 855 [MꢁH]ꢁ; m/z 635 [Mmono+Cl]ꢁ; m/z 255
[L4]ꢁ, 100%; m/z 211 [L4-CO2]ꢁ. MS/MS of m/z 855: m/z
255 [L4]ꢁ. 119Sn Mo¨ssbauer: d = 1.49, D = 3.51, C1 = 0.80,
C2 = 0.83 mm sꢁ1, q = 2.36, C–Sn–C = 143ꢁ.
443
[Mmono+Hꢁoctane–CO2]+;
m/z
375
[Mmono
2.4.5. {[nOct2Sn(L5H)]2O}2 (5)
2.4.3. {[nOct2Sn(L2H)]2O}2 (3)
Compound 5 was prepared by following the method
and conditions described for 1 and using L5HH0 (0.50 g,
1.81 mmol) and nOct2SnO (0.65 g, 1.81 mmol). The
dried orange product was recrystallized from hot hexane.
Yield: 0.61 g, 55%. m.p.: 74–76 ꢁC. Anal. Calc. for
Orange prismatic crystals of compound 3, m.p.
74–76 ꢁC, were obtained from petroleum ether in 50%
yield. Anal. Calc. for C120H180N8O18Sn4: C, 57.71; H,
7.26; N, 4.49. Found: C, 57.65; H, 7.30; N, 4.52%. IR
(KBr, cmꢁ1): 1622 m(OCO)asym, 620 m(Sn–O–Sn). For
NMR: refer to Section 3.2 for specific comments. ESI-
MS: MW = 2500. Mmono = 616 = L2SnOct2-H. Positive-
ion MS: m/z 1233 [2*Mmono+H]+; m/z 927 [Mmono
+K+L2H]+; m/z 911 [Mmono+Na+L2H]+; m/z 655 [Mmono
+K]+; m/z 639 [Mmono+Na]+; m/z 617 [Mmono+H]+. MS/
MS of m/z 617: m/z 599 [Mmono+HꢁH2O]+; m/z 573 [Mmo-
no+HꢁCO2]+; m/z 391 [Mmono+Hꢁoctene–octane]+; m/z
347 [Mmono+Hꢁoctene–octane–CO2]+. Negative-ion MS:
m/z 2517 [MꢁH+H2O]ꢁ; m/z 2499 [MꢁH]ꢁ; m/z
2391 [3*Mmono+L2+L2H]ꢁ; m/z 2119 [3*Mmono+L2]ꢁ;
m/z 1775 [2*Mmono+L2+L2H]ꢁ; m/z 1539 [2*Mmono
+Cl+L2H]ꢁ; m/z 1503 [2*Mmono+L2]ꢁ; m/z 1267
[2*Mmono+Cl]ꢁ; m/z 1159 [Mmono+L2+L2H]ꢁ; m/z 887
[Mmono+L2]ꢁ; m/z 651 [Mmono+Cl]ꢁ; m/z 271 [L2]ꢁ,
100%; m/z 227 [L2-CO2]ꢁ; m/z 212 [L2–CH3OH–N2]ꢁ.
MS/MS of m/z 2499: m/z 2481 [MꢁH–H2O]ꢁ; m/z 2227
[MꢁH–L2H]ꢁ; m/z 1883 [MꢁH–Mmono]ꢁ; m/z 1865
[MꢁH–Mmono–H2O]ꢁ; m/z 1611 [MꢁH–L2H–Mmono]ꢁ;
m/z 1249 [MꢁH-2*Mmono-H2O]ꢁ; m/z 887 [Mmono+L2]ꢁ.
MS/MS of m/z 2391: m/z 2119 [3*Mmono+L2]ꢁ; m/z 1775
[2*Mmono+L2+L2H]ꢁ; m/z 1503 [2*Mmono+L2]ꢁ; m/z
887 [Mmono+L2]ꢁ. MS/MS of m/z 887: m/z 271 [L2]ꢁ.
119Sn Mo¨ssbauer: d = 1.33, D = 3.41, C1 = 0.78,
C2 = 0.78 mm sꢁ1, q = 2.56, C–Sn–C = 140ꢁ.
C
116H168N8O12Cl4Sn4: C, 56.11; H, 6.82; N, 4.51. Found:
C, 56.15; H, 6.86; N, 4.54%. IR (KBr, cmꢁ1): 1628
m(OCO)asym 615m(Sn–O–Sn). 1H NMR (CDCl3, 300.
13 MHz); dH: Ligand skeleton: 7.08 [d, 1H, H-3], 7.30 [d,
2H, H-20 and H-60], 7.73 [d, 2H, H-30 and H-50], 8.10
[dd, 1H, H-4], 8.37 [d, 1H, H-6], 11.75 [brs, 1H, OH];
Sn-nOct skeleton: 0.77 [brm, 6H, CH3], 0.80–2.0 [brm,
28H, CH2], ppm. 13C NMR (CDCl3, 75.47 MHz); dC:
Ligand skeleton: 114.4 [C-1], 118.6 [C-3], 124.0 [C-20 and
C-60], 126.7 [C-6], 129.3 [C-30 and C-50], 136.5 [C-4],
145.1 [C-40], 150.6 [C-5], 155.3 [C-10], 164.7 [C-2], 175.5
[CO2]; Sn-nOct skeleton: 14.3 [CH3], 22.7, 25.2, 25.4, 25.7,
27.4, 29.3, 29.8, 30.2, 31.9, 33.9, 34.0 [CH2 carbons],
ppm. 119Sn NMR (CDCl3, 111.92 MHz); dSn: ꢁ187.2 and
ꢁ189.7 ppm. ESI-MS: MW = 2516. Mmono = 620 = LS-
nOct2-H. Positive-ion MS: m/z 621 [Mmono+H]+; m/z 459
[SnOct3]+. Negative-ion MS: m/z 2533 [MꢁH+H2O]ꢁ;
m/z 2515 [MꢁH]ꢁ; m/z 2411 [3*Mmono+L5+LH]ꢁ; m/z
2249 [2*Mmono+L5+L5SnOct3]ꢁ; m/z 2135 [3*Mmono+L5]ꢁ;
m/z 1791 [2*Mmono+L5+L5H]ꢁ; m/z 1629 [Mmono+L5
+L5SnOct3]ꢁ; m/z 1551 [2*Mmono+Cl+L5H]ꢁ; m/z 1515
[2*Mmono+L5]ꢁ; m/z 1275 [2*Mmono+Cl]ꢁ; m/z 1009
[L5SnOct3+L5]ꢁ; m/z 895 [Mmono+L5]ꢁ; m/z 655
[Mmono+Cl]ꢁ; m/z 275 [L5]ꢁ, 100%; m/z 231 [L5ꢁCO2]ꢁ.
MS/MS of m/z 2515: m/z 2497 [MꢁH–H2O]ꢁ; m/z 2239