330 Herna´ndez-D´ıaz, Flores-Parra, and Contreras
111.0 (d, 3 JPC 10.9 Hz, C7), 135.8 (d, 2 JPC 22.1 Hz, C8),
144.4 (d, 3 JPC 4.1 Hz, C9), 121.8 (d, 3 JPC 5.9 Hz, C10),
138.1 (t, 2 JPC 2.5 Hz, C11), 123.5 (dd, 3 JPC 4.7 and 3 JPC
1.3 Hz, C12), 130.7 (C13), 124.6 (C14), 127.0 (C15),
39.4 (d, 2 JPC 20.9 Hz, P N(CH3)2), 38.9 (d, 2 JPC 8.7 Hz,
149.6 (C2), 120.0 (C4), 123.7 (C5), 124.0 (C6), 110.0
(d, 3 JPC 6.2 Hz, C7), 136.6 (d, 2 JPC 20.0 Hz, C8), 144.3
2
(C9), 123.4 (C10), 135.9 (dd, JPC 16.9 and 6.7 Hz,
3
C11), 124.8 (d, JPC 4.6 Hz, C12), 130.0 (C13), 125.4
4
(C14), 127.4 (C15), 137.9 (Ci), 132.7 (d, JPC 3.1 Hz,
4
2
1
Co), 132.1 (d, JPC 3.1 Hz, Co), 128.7 (Cm), 128.4
P[N(CH3)2]2), 38.9 (d, JPC 8.3 Hz, P[N(CH3)2]2). H
NMR (CDCl3): δ 7.85 (d, JHH 7.41 Hz, H4), 7.33 (dd,
JHH 7.41 and 7.30 Hz, H5), 7.30 (dd, JHH 7.30 and
7.69 Hz, H6), 7.69 (d, JHH 7.40 Hz, H7), 8.04 (d, JHH
8.32 Hz, H12), 7.43 (dd, JHH 7.34 and 8.32 Hz, H13),
7.28 (dd, JHH 7.77 and 7.32 Hz, H14), 8.39 (d, JHH
1
(Cm), 129.9 (Cp) (P Ph), 135.4 (d, JPC 7.7 Hz, Ci),
135.2 (d, 1 JPC 7.7 Hz, Ci), 133.0 (d, 2 JPC 12.3 Hz, Co),
132.5 (d, 2 JPC 10.0 Hz, Co), 128.6 (d, 3 JPC 3.1 Hz, Cm),
128.5 (Cm), 129.6 (Cp), 129.4 (Cp) (P Ph2). 1H NMR
(CDCl3): δ 8.00 (d, JHH 7.32 Hz, H4), 7.43 (dd, JHH 7.16
and 6.60 Hz, H5), 7.31–7.38 (m, H6, H7), 7.63 (d, JHH
8.04 Hz, H12), 6.94 (dd, JHH 8.04 and 7.32 Hz, H13),
7.03 (dd, JHH 7.72 and 7.32 Hz, H14), 8.22 (d, JHH
7.68 Hz, H15), 7.47–7.51 (m, Ho), 7.31–7.38 (m, Ho,
Hm), 7.16–7.27 (m, Hm), 7.08–7.14 (m, Hp) (P Ph),
3
7.77 Hz, H15), 2.38 (d, JPC 10.73 Hz, P N(CH3)2),
3
3
2.82 (d, JPH 10.92 Hz, P[N(CH3)2]2), 2.54 (d, JPH
11.37 Hz, P[N(CH3)2]2). 77Se NMR: −207.8 (dd, 1 JPSe
3
829.7 and JPSe 8.6 Hz). MS: m/z (%): 480.20 (3)
[M]+, 362.15 (4), 298.20 (3), 238.15 (28), 237.15 (15),
199.15 (12), 119.15 (100).
3
8.00 (dd, JPH 14.27 and JHH 6.96 Hz, Ho), 7.82 (dd,
3 JPH 13.91 and JHH 7.32 Hz, Ho), 7.31–7.38 (m, Hm),
7.08–7.14 (Hm, Hp, Hp). 77Se NMR: −181.8 (dd, 1 JPSe
792.6 and 3 JPSe 6.1 Hz). MS: m/z (%): 579.10 (1) [M]+,
395.00 (39), 393.05 (22), 391.05 (23), 315.20 (22),
314.10 (39), 269.20 (16), 238.15 (100), 186.15 (24),
108.05 (30).
5-Diphenylthiophosphinoyl-6-phenyl-5,6a,11-
triaza-6-phospha-benzo[a]fluorene (18)
It was obtained from reaction of 480 mg (0.96 mmol)
of 11 in toluene and 31 mg (0.96 mmol) of sulfur,
and stirring overnight at rt. 31P NMR showed quan-
titative formation of 18. It was not isolated due to its
great fragility and it was immediately used to prepare
compound 20. 13C NMR (CDCl3): δ 49.7 (C2), 120.1
5-Diphenylthiophosphinoyl-6-thioxo-6-phenyl-
5,6a,11-triaza-6-phospha-benzo[a]fluorene (20)
3
(C4), 123.8 (C5), 124.1 (C6), 111.1 (d, JPC 6.9 Hz,
This compound was prepared by adding 12 mg (0.38
mmol) of sulfur to a toluene solution of 200 mg (0.38
mmol) of 18 prepared freshly. After heating at re-
flux for 1 h, the reaction mixture was filtered and
the solvent evaporated in vacuum to afford 198 mg
(93%) of a yellow solid. mp 130–134◦C. Compound
20 was also obtained reacting compound 11 with an
excess of sulfur for 1 h in refluxing toluene. 13C NMR
(CDCl3): δ 150.6 (C2), 120.3 (C4), (C5), (C6), 114.2
2
C7), 136.8 (d, JPC 19.4 Hz, C8), 144.3 (C9), 123.0
2
(C10), 136.2 (dd, JPC 15.8 and 5.7 Hz, C11), 125.1
(d, 3 JPC 4.2 Hz, C12), 130.3 (C13), 125.4 (C14), 127.5
4
(C15), 138.0 (Ci), 132.6 (d, JPC 2.7 Hz, Co), 132.1
4
(d, JPC 2.7 Hz, Co), 128.9 (Cm), 128.5 (Cm), 129.9
(Cp) (P Ph), 133.8 (d, 1 JPC 6.0 Hz, Ci), 132.8 (d, 2 JPC
10.6 Hz, Co), 132.4 (dd, 2 JPC 11.0 and 4 JPC 3.3 Hz, Co),
128.7 (d, 3 JPC 3.5 Hz, Cm), 128.7 (d, 3 JPC 4.3 Hz, Cm),
1
129.5 (Cp), 129.3 (Cp) (P Ph2). H NMR (CDCl3): δ
2
3
(C7), 136.6 (d, JPC 5.7, C8), 144.6 (d, JPC 11.1 Hz,
C9), 124.8 (C10), (d, 2 JPC 2.9 Hz, C11), 128.0 (dd, 3 JPC
5.4 and 4.5 Hz, C12), 130.1 (C13), 127.0 (C14), 127.5
(C15), 134.3 (d, 1 JPC 42.3 Hz, Ci), 132.1 (dd, 2 JPC 12.2
and 4 JPC 2.8 Hz, Co), 128.9 (d, 3 JPC 15.8 Hz, Cm), 131.8
(Cp) (P Ph), 135.8 (d, 1 JPC 12.2 Hz, Ci), 132.6 (d, 2 JPC
7.98–8.05 (m, H4), 7.44 (dd, JHH 6.41 and 6.70 Hz,
H5), 7.30–7.42 (m, H6, H7), 7.65 (d, JHH 7.94 Hz,
H12), 6.95 (dd, JHH 7.50 and 7.97 Hz, H13), 7.03 (dd,
JHH 7.44 and 7.60 Hz, H14), 8.22 (d, JHH 7.47 Hz,
H15), 7.50–7.54 (m, Ho), 7.30–7.42 (m, Ho, Hm),
7.18–7.28 (m, Hm), 7.08–7.14 (m, Hp) (P Ph), 7.98–
8.05 (m, Ho), 7.75–7.82 (m, Ho), 7.30–7.42 (m, Hm),
7.08–7.14 (m, Hm, Hp, Hp) (P Ph2). MS: m/z (%):
531.20 (14) [M]+, 392.20 (35), 391.20 (100), 347.20
(12), 314.25 (17), 238.25 (10), 217.25 (43), 139.15
(14).
2
10.7 Hz, Co), 131.7 (d, JPC 11.5 Hz, Co), 128.5 (d,
3
3 JPC 8.4 Hz, Cm), 128.3 (d, JPC 8.1 Hz, Cm), 129.3
(Cp), 129.2 (Cp) (PPh2). 1H NMR (CDCl3): δ 7.99 (d,
JHH 8.34 Hz, H4), 7.48 (dd, JHH 8.16 and 7.38 Hz,
H5), 7.39 (dd, JHH 7.32 and 8.18 Hz, H6), 8.33 (d,
JHH 8.07 Hz, H7), 7.00 (d, JHH 8.30 Hz, H12), 6.78
(dd, JHH 7.27 and 7.42 Hz, H13), 7.05 (dd, JHH 7.35
and 7.90 Hz, H14), 8.15 (d, JHH 7.66 Hz, H15), 7.16–
7.36 [m, H(o), H(m), H(p)] (P Ph), 7.87–7.94 [m,
H(o)], 7.16–7.36 [m, H(m), H(p)] (P Ph2). MS: m/z
(%): 563.20 (22) [M]+, 454.15 (11), 423.20 (7), 391.20
(6), 347.20 (16), 314.20 (8), 218.20 (17), 217.20 (100),
139.15 (22).
5-Diphenylselenophosphinoyl-6-phenyl-5,6a,11-
triaza-6-phospha-benzo[a]fluorene (19)
It was prepared using the same procedure as for 18
from 480 mg (0.96 mmol) of 11 and 76 mg (0.96
mmol) of selenium. The reaction was quantitative.
Compound 19 was not isolated. 13C NMR (CDCl3): δ