110.71, 125.69, 128.56, 129.33, 131.21 (d, J = 1.8 Hz), 131.41,
131.54, 132.28, 132.42, 136.04, 137.08, 137.76, 137.90, 140.74,
149.00, 154.00, 161.39. 31P NMR (C6D6+C5D5N): d 26.94.
138.08, 138.28, 159.00, 159.12, 159.26, 159.37. 31P NMR (CDCl3):
d -14.99 (m), -7.57.
=
=
2-(p-MeC6H4N PPh2)-6-(Me3SiN PPh2CH2)C5H3N
(8b).
[Pb2{C(Ph2P NSiMe3){6-(2-(3,5-Me2C3HN2)C5H3N)}}2] (4).
A mixture of 7b (0.44 g, 0.78 mmol) and Me3SiN3 (0.20 cm3,
1.5 mmol) was heated at 140–160 ◦C for 12 h with stirring.
Excess Me3SiN3 was removed in vacuo and the residue was
dissolved in CH2Cl2. The solution was filtered and the filtrate was
concentrated to about 2 cm3. Hexane (10 cm3) was added and set
aside overnight to give yellow crystals of 8b (0.32 g, 63%) (found:
C, 70.30; H, 6.07; N, 6.39. C40H41N3P2Si·0.4CH2Cl2 requires C,
70.55; H, 6.13; N, 6.11%), mp 92–94 ◦C.1H NMR (CDCl3): -0.21
(s, 9H, SiMe3), 2.09 (s, 3H, Me), 3.79 (d, J = 14.1 Hz, 2H, CH2),
6.60 (d, J = 8.2 Hz, 2H, Ar), 6.73 (d, J = 8.1 Hz, 2H, Ar),
7.09–7.15 (m, 4H, Ar), 7.23–7.28 (m, 6H, Ar), 7.35–7.40 (m, 3H,
Ar), 7.44–7.58 (m, 5H, Ar), 7.63–7.70 (m, 4H, Ar), 8.01–8.06 (m,
1H, Py). 13C NMR (CDCl3): d 3.97 (d, J = 3.3 Hz), 20.63, 42.76
(d, J = 66.6 Hz), 120.08, 123.14, 123.38, 126.29, 127.00 (d, J =
3.3 Hz), 127.04 (d, J = 3 Hz), 127.25 (d, J = 2.3 Hz), 127.51
(d, J = 2.6 Hz), 128.21 (d, J = 9.6 Hz), 128.36 (d, J = 9.6 Hz),
129.35 (d, J = 1.7 Hz), 130.09, 130.86 (d, J = 2.8 Hz), 131.11,
131.24, 131.38, 131.44 (d, J = 2.8 Hz), 133.08 (d, J = 9.4 Hz),
=
To a slolution of 2 (0.36 g, 0.79 mmol) in toluene (20 cm3) was
added a solution of Pb[N(SiMe3)2]2 (0.44 g, 0.83 mmol) in toluene
(5 cm3) at room temperature with stirring. The mixture was stirred
at room temperature for 72 h and then filtered. Concentration of
the filtrate afforded red crystals identified as 4·0.8PhMe (0.32 g,
58%) (found: C, 49.40; H, 4.56; N, 8.13. C52H58N8P2Pb2Si2·0.8C7H8
◦
1
requires C, 49.30; H, 4.63; N, 7.99%), mp 178–180 C (dec). H
NMR (C5D5N): d -0.11 (s, 9H, SiMe3), 0.28 (s, 9H, SiMe3), 1.93 (s,
3H, Me), 2.20 (s, 3H, Me), 2.26 (s, PhMe), 2.35 (s, 3H, Me), 2.40 (s,
3H, Me), 5.64 (s, 1H, pyrazolyl), 5.80 (d, J = 7.8 Hz, 1H, Py), 5.86
(d, J = 7.8 Hz, 1H, Py), 5.93 (s, 1H, pyrazolyl), 6.50 (d, J = 7.5 Hz,
1H, Ar), 6.83 (t, J = 8 Hz, 1H, Ar), 7.09–7.32 (m, 18H, Ar), 7.87–
7.97(m, 8H, Ar). 13C NMR (C5D5N): d 1.42, 3.66 (d, J = 3.1 Hz),
13.37, 13.98, 14.24, 14.51, 21.42, 104.07, 107.99, 108.26, 109.07,
109.45, 109.72, 125.70, 127.91, 128.57, 128.66, 129.34, 130.24 (d,
J = 4.7 Hz), 130.58, 130.84, 130.98, 131.19, 131.32, 134.90, 136.88,
137.90, 138.78, 140.04, 141.06, 144.56, 145.43, 145.62, 146.53,
148.74, 149.03, 149.17, 151.89, 158.75, 161.82. 31P NMR (C5D5N):
d 3.17, 12.32.
134.76, 135.93, 136.06, 148.46 (d, J = 2.6 Hz), 155.19, 155.29. 31
NMR (CDCl3): -6.77, -3.96 (m).
P
=
=
=
2-(p-MeC6H4N PPh2)-6-MeC5H3N (6b). To a stirred solu-
[Sn2{C(Ph2P NSiMe3){6-(2-(PPh2 NSiMe3)C5H3N)}}2] (9).
To a solution of 8a (0.18 g, 0.28 mmol) in toluene (10 cm3) was
added a solution of Sn[N(SiMe3)2]2 (0.14 g, 0.31 mmol) in toluene
(5 cm3) at room temperature with stirring. The mixture was kept
stirring at room temperature for 24 h and then refluxed for 6 h.
The hot solution was filtered and the filtrate was cooled to room
temperature to afford yellow crystals of 9 (0.14 g, 66%) (found:
C, 57.34; H, 5.55; N, 5.39. C72H82N6P4Si4Sn2 requires C, 57.46;
tion of 5 (0.40 g, 1.44 mmol) in THF (10 cm3) was added
dropwise p-MeC6H4N3 (0.23 g, 1.73 mmol) at room temperature.
The solution color changed to pale yellow. The mixture continued
to stir for 3 h. Solvent was removed in vacuo and the residue
was dissolved in Et2O. The ether solution was filtered and the
filtrate was concentrated to give pale yellow powder (0.40 g, 73%)
(found: C, 78.50; H, 6.09; N, 7.20. C25H23N2P requires C, 78.51;
◦
◦
1
1
H, 6.06; N, 7.32%), mp 149–150 C. H NMR (CDCl3): 2.12 (s,
3H, Me), 2.50 (s, 3H, Me), 6.65–6.77 (m, 3H, Ar), 7.11–7.14 (m,
1H, Ar), 7.30–7.43 (m, 7H, Ar), 7.83–8.02 (m, 6H, Ar). 13C NMR
(CDCl3): d 20.62, 24.72, 123.19, 123.43, 124.81, 126.18, 126.38,
126.65, 128.33 (d, J = 11.8 Hz), 129.34, 130.38, 131.47, 131.67,
133.07 (d, J = 9.1 Hz), 136.19 (d, J = 9.7 Hz), 148.62, 153.54,
155.24, 159.00, 159.25. 31P NMR (CDCl3): d -7.78.
H, 5.49; N, 5.58%), mp 220–222 C. H NMR (C6D6+THF): d
-0.86 (s, 9H, SiMe3), 0.06 (d, J = 1.8 Hz, 9H, SiMe3), 6.95–
6.99 (m, 1H, Py), 7.05–7.31 (m, 14H, Ar), 7.35–7.42 (m, 2H, Ar),
7.62–7.68 (m, 2H, Ar), 7.83–8.02 (m, 2H, Ar), 8.15–8.21 (m, 2H,
Ar). 13C NMR(C6D6+THF): 1.77, 3.99 (d, J = 3.4 Hz), 120.49,
121.73, 122.04, 125.64, 126.40, 126.67, 127.93, 128.16, 128.22,
128.51, 128.59, 129.28, 130.11 (d, J = 1.9 Hz), 130.83 (d, J =
2.9 Hz), 131.35, 131.47, 133.60, 133.72, 134.36, 135.11, 135.20,
135.85, 136.53, 137.15, 138.83, 139.22, 157.43, 159.08. 31P NMR
(C6D6+THF):d -7.91 (m), 30.24 (m).
=
2-(p-MeC6H4N PPh2)-6-(CH2PPh2)C5H3N (7b). A solution
of 6b (0.55 g, 1.44 mmol) in THF (30 cm3) was cooled to about
-60 ◦C. To the solution was added LDA (1.8 mmol) prepared
from Pri2NH (0.37 cm3, 1.85 mmol) and BunLi (0.72 cm3, 2.5 M,
1.8 mmol). The mixture was stirred at -20 ◦C for 20 min and re-
cooled to about -80 ◦C. To the cooled solution Ph2PCl (0.32 cm3,
1.8 mmol) in THF (5 cm3) was added. The solution was stirred
at -80 ◦C for 15 min and at room temperature overnight. Solvent
was removed in vacuo and the residue was extracted with diethyl
ether. The extract was filtered and the filtrate was concentrated
to afford yellow crystals of 7b (0.44 g, 54%) (found: C, 78.06; H,
5.83; N, 4.75. C37H32N2P requires C, 78.43; H, 5.69; N, 4.94%), mp
78–80 ◦C. 1H NMR (CDCl3): d 2.11 (s, 3H, Me), 3.58 (s, 2H, CH2),
6.63 (d, J = 8.1 Hz, 1H, Py), 6.74 (d, J = 8.1 Hz, 1H, Py), 7.06–7.54
(m, 20H, Ar), 7.67–7.83 (m, 4H, Ar), 7.98 (t, J = 6.6 Hz, 1H, Py).
13C NMR (CDCl3): d 20.65, 38.74 (d, J = 16.7 Hz), 123.21 (d, J =
18.3 Hz), 125.22 (d, J = 3.5 Hz), 125.29 (d, J = 3.5 Hz), 126.27,
126.74, 127.00, 128.28, 128.44, 128.53, 128.78, 129.35, 131.47 (d,
J = 2.6 Hz), 132.69, 132.95, 133.05, 133.17, 136.36 (d, J = 9.6 Hz),
=
=
[Pb2 {C(Ph2P NSiMe3){6-(2-(PPh2 NSiMe3)C5H3N)}}2 ]
(10). A similar procedure to 9 was followed. Thus, to a solution
of 8a (0.14 g, 0.22 mmol) in toluene (10 cm3) was added a solution
of Pb[N(SiMe3)2]2 (0.14 g, 0.27 mmol) in toluene (5 cm3) at room
temperature with stirring. The mixture was kept stirring at room
temperature for 24 h and then refluxed for 6 h. The hot solution
was filtered and the filtrate was cooled to room temperature to
precipitate red crystals of 10 (0.08 g, 43%) (found: C, 51.19; H,
4.91; N, 5.00. C72H82N6P4Pb2Si4 requires C, 51.41; H, 4.91; N,
5.00%), mp 103–105 ◦C. 1H NMR (C6D6+THF): d -0.04 (d, J =
3 Hz, 9H, SiMe3), -0.05 (d, J = 3.3 Hz, 9H, SiMe3), 6.81–6.87 (m,
1H, Ar), 6.95–7.23 (m, 16H, Ar), 7.42–7.76 (m, 4H, Ar), 8.12 (t,
J = 7.5 Hz, 2H, Ar). 13C NMR(C6D6+THF): 1.17, 4.11, 126.39,
126.73, 126.89, 128.22, 128.65, 126.82, 129.28, 130.46 (d, J =
11.8 Hz), 130.84 (d, J = 2.8 Hz), 131.12, 131.35, 131.49, 131.84,
131.98, 132.63, 132.76, 133.02, 134.53, 135.20, 135.86, 136.53,
8010 | Dalton Trans., 2009, 8005–8012
This journal is
The Royal Society of Chemistry 2009
©