Preparation of [{(SiMe3)(Ar*)N}GeCl] 4. LiBun (1.9 cm3
of a 1.6 M solution in hexane) was added to a solu◦tion of
Ar*N(H)SiMe3 (1.50 g, 2.9 mmol) in THF (50 cm3) at -80 C over
5 min. The reaction mixture was warmed to room temperature
and stirred for 1 h. This solution was then added to a solution of
GeCl2·dioxane (0.75 g, 3.2 mmol) in THF (10 cm3) at -80 ◦C. The
resultant solution was warmed to room temperature and stirred for
3 h, whereupon volatiles were removed in vacuo. The residue was
extracted with toluene (60 cm3), the extract filtered and volatiles
removed in vacuo to give 4 as a pale yellow solid (1.29 g, 72%).
N.B. X-ray quality crystals of 4 were obtained by recrystallising
this solid from diethyl ether. Mp: 254–258 ◦C; 1H NMR (400 MHz,
C6D6, 298 K): d = 0.71 (s, 9H, SiMe3), 1.87 (s, 3H, ArCH3), 5.89
(s, 2H, Ph2CH), 6.92 (s, 2H, m-ArH), 6.89–7.24 (m, 20H, ArH);
3 h, whereupon volatiles were removed in vacuo. The residue was
extracted with toluene (30 cm3), the extract filtered and volatiles
removed in vacuo to give 7 as a pale yellow solid (0.41 g, 61%).
N.B. X-ray quality crystals of 7 were obt◦ained by recrystallising
this solid from diethyl ether. Mp: 242–244 C (decomp.); 1H NMR
(400 MHz, C6D6, 298 K): d = 0.76 (s, 9H, SiMe3), 1.91 (s, 3H,
1
ArCH3), 6.04 (s, 2H, Ph2CH), 6.74–7.24 (m, 22H, ArH); 13C{ H}
NMR (101 MHz, C6D6) d = 5.0 (Si(CH3)3), 21.3 (ArCH3), 53.6
(Ph2CH), 126.9, 128.6, 129.4, 130.0, 130.6, 131.6, 132.8, 143.3,
1
144.4, 145.0 (Ar–C); 29Si{ H} NMR (80 MHz, C6D6) d = 3.9 (s);
1
119Sn{ H} NMR (149 MHz, C6D6) d = 173.7; IR n/cm-1 (Nujol):
1600(m), 1492(m), 1378(m), 1246(m), 1030(s), 920(m), 702(s);
MS/EI m/z (%): 665.2 (MH+, 9, correct isotopic distribution),
510.3 (M+-SnCl, 100), 439.2 (Ar*NH2 , 8), 167.0 (CHPh2 , 15);
acc. mass MS (EI) m/z: calc for C36H36Cl116GeNSi: 661.1317,
found: 661.1317.
+
+
1
13C{ H} NMR (101 MHz, C6D6) d = 4.5 (Si(CH3)3), 21.3 (ArCH3),
53.7 (Ph2CH), 126.9, 128.7, 130.0, 130.1, 131.2, 134.6, 142.0, 143.2,
1
143.4, 145.0 (Ar-C); 29Si{ H} NMR (80 MHz, C6D6) d = 5.9 (s);
Preparation of [{(SiMePh2)(Ar*)N}SnCl] 8. Compound 8 was
prepared using a similar procedure to that employed for 7. Pale
yellow crystalline solid (yield: 55%). Mp: 240–248 ◦C (decomp.);
1H NMR (400 MHz, C6D6, 298 K): d = 1.52 (s, 3H, SiMe), 1.90
(s, 3H, ArCH3), 5.91 (s, 2H, Ph2CH), 6.90 (s, 2H, m-ArH), 6.73–
IR n/cm-1 (Nujol): 1596(m), 1492(m), 1377(m), 1248(m), 1032(s),
919(m), 697(s); MS/EI m/z (%): 619.2 (M+, 8), 510.2 (M+-GeCl,
+
+
100), 439.2 (Ar*NH2 , 12), 167.0 (CHPh2 , 12); acc. mass MS (EI)
m/z: calc for C36H36Cl70GeNSi: 615.1543, found: 615.1546; anal.
calc. for C36H36ClGeNSi: C 69.87%, H 5.86%, N 2.26%, found: C
69.82%, H 5.99%, N 2.15%.
1
7.97 (m, 30H, ArH); 13C{ H} NMR (101 MHz, C6D6) d = 7.0
(Si(CH3)), 25.8 (ArCH3), 57.7 (Ph2CH), 126.5, 128.2, 128.7, 129.5,
129.8, 130.6, 131.6, 136.3, 140.0, 143.0, 144.5, 146.0 (br, Ar-C);
Preparation of [{(SiMePh2)(Ar*)N}GeCl] 5. Compound 5 was
prepared using a similar procedure to that employ◦ed for 4. Pale
1
1
29Si{ H} NMR (80 MHz, C6D6) d = -11.6 (s); 119Sn{ H} NMR
(149 MHz, C6D6) d = 104.5; IR n/cm-1 (Nujol): 1598(m), 1455(m),
1377(m), 1261(m), 1031(s), 914(m), 699(s); MS/EI m/z (%): 789.1
(M+, 8, correct isotopic distribution), 634.3 (M+-SnCl, 100), 439.2
1
yellow crystalline solid (yield: 66%). Mp: 234–240 C; H NMR
(400 MHz, C6D6, 298 K): d = 1.38 (s, 3H, SiMe), 1.86 (s, 3H,
ArCH3), 5.89 (s, 2H, Ph2CH), 6.91 (s, 2H, m-ArH), 6.95–7.97 (m,
+
1
30H, ArH); 13C{ H} NMR (101 MHz, C6D6) d = 2.4 (Si(CH3)),
(Ar*NH2 , 75).
21.4 ArCH3), 53.2 (Ph2CH), 126.7, 128.2, 128.4, 129.9, 130.0,
Preparation of [{(SiPh3)(Ar*)N}SnCl] 9. Compound 9 was
prepared using a similar procedure to that employed for 7. Pale
yellow crystalline solid (yield: 48%). Mp: 224–228 ◦C (decomp.);
1H NMR (400 MHz, C6D6, 298 K): d = 1.91 (s, 3H, ArCH3), 6.32
(s, 2H, Ph2CH), 6.87 (s, 2H, m-ArH), 6.75–8.21 (m, 35H, ArH);
1
130.1, 131.5, 135.1, 136.6, 138.4, 143.4, 145.6 (br, Ar-C); 29Si{ H}
NMR (80 MHz, C6D6) d = -10.6 (s); IR n/cm-1 (Nujol): 1597(m),
1456(m), 1377(m), 1261(m), 1029(s), 912(m), 699(s); MS/EI m/z
+
(%): 743.2 (MH+, 15), 634.3 (M+-GeCl, 100), 439.2 (Ar*NH2 ,
100); acc. mass MS (EI) m/z: calc for C46H40Cl70GeNSi: 739.1856,
1
13C{ H} NMR (101 MHz, C6D6) d = 15.6 (ArCH3), 65.9 (Ph2CH),
found: 739.1852.
126.5, 128.3, 128.4, 129.8, 130.3, 131.4, 136.4, 137.6, 142.7, 143.5,
1
Preparation of [{(SiPh3)(Ar*)N}GeCl] 6. Compound 6 was
prepared using a similar procedure to that employ◦ed for 4. Pale
145.3, 145.7 (Ar-C); 29Si{ H} NMR (80 MHz, C6D6) d = -15.7
(s); 119Sn{1H} NMR (149 MHz, C6D6) d = 185.4; IR n/cm-1
(Nujol): 1598(m), 1455(m), 1377(m), 1259(m), 1030(s), 912(m),
700(s); MS/EI m/z (%): 851.2 (M+, 4), 697.4 (M+-SnCl, 100), 439.2
1
yellow crystalline solid (yield: 67%). Mp: 136–140 C; H NMR
(400 MHz, C6D6, 298 K): d = 1.86 (s, 3H, ArCH3), 6.21 (s,
2H, Ph2CH), 6.90 (s, 2H, m-ArH), 6.82–8.23 (m, 35H, ArH);
+
(Ar*NH2 , 10); acc. mass MS (EI) m/z: calc for C51H42Cl116SnNSi:
1
13C{ H} NMR (101 MHz, C6D6) d = 21.2 (ArCH3), 52.5 (Ph2CH),
847.1787, found: 847.1793.
126.5, 128.2, 128.5, 129.3, 129.9, 131.3, 135.2, 137.6, 140.3, 143.6,
Preparation of [{[(SiMe3)(Ar*)N]PbCl}2] 10. LiBun (0.64 cm3
of a 1.6 M solution in hexane) was added to a solu◦tion of
Ar*N(H)SiMe3 (0.50 g, 1.0 mmol) in THF (20 cm3) at -80 C over
5 min. The reaction mixture was warmed to room temperature and
stirred for 1 h. This solution was then added to a suspension of
PbCl2 (0.30 g, 1.1 mmol) in THF (10 cm3) at -80 ◦C. The resultant
solution was warmed to room temperature, whereupon volatiles
were removed in vacuo. The residue was extracted with toluene (25
cm3), the extract filtered and volatiles removed in vacuo to give 10
as a pale yellow solid (0.39 g, 41%). N.B. X-ray quality crystals of
10 were obtained by recrystallising this solid from toluene. Mp:
117–123 ◦C (decomp.). N.B. The compound slowly decomposes
1
144.2, 145.9 (Ar-C); 29Si{ H} NMR (80 MHz, C6D6) d = -15.6
(s); IR n/cm-1 (Nujol): 1598(m), 1458(m), 1377(m), 1259(m),
1031(s), 910(m), 699(s); MS/EI m/z (%): 805.2 (M+, 3), 697.3
(M+-GeCl, 100), 439.2 (Ar*NH2 , 40); acc. mass MS (EI) m/z:
+
calc for C51H42Cl70GeNSi: 801.2012, found: 801.2010; anal. calc.
for C51H42ClGeNSi: C 76.09%, H 5.26%, N 1.74%, found: C
76.05%, H 5.62%, N 1.54%.
Preparation of [{(SiMe3)(Ar*)N}SnCl] 7. LiBun (0.65 cm3
of a 1.6 M solution in hexane) was added to a solu◦tion of
Ar*N(H)SiMe3 (0.50 g, 1.0 mmol) in THF (20 cm3) at -80 C over
5 min. The reaction mixture was warmed to room temperature
and stirred for 1 h. This solution was then added to a suspension
of SnCl2 (0.20 g, 1.0 mmol) in THF (10 cm3) at -80 ◦C. The
resultant solution was warmed to room temperature and stirred for
1
at room temperature; H NMR (400 MHz, C6D6, 298 K): d =
0.80 (s, 18H, SiMe3), 2.07 (s, 6H, ArCH3), 6.31 (s, 4H, Ph2CH),
1
6.97 (s, 4H, m-ArH), 6.76–7.24 (m, 40H, ArH); 13C{ H} NMR
10454 | Dalton Trans., 2011, 40, 10448–10456
This journal is
The Royal Society of Chemistry 2011
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