Dalton Transactions
Paper
3
J
PH 15.1 Hz, H25), 7.01 (m, 2H, H15), 7.10 (m, 2H, H21), 7.18
Complex 21a. Yield after recrystallization 61% (39 mg).
1
(m, 1H, H16), 7.22 (m, 2H, H20), 7.28 (m, 1H, H22), 7.36 (m, White solid. Mp: 285–286 °C. H NMR δ (CDCl , 500.13 MHz) δ
3
3
3
2
H, H14), 7.37 (m, 2H, H9), 7.45 (m, 1H, H10), 7.73 (m, 1H, 1.02 (d, 6H, JHH 6.8 Hz, H26/27), 1.25 (d, 6H, JHH 6.8 Hz,
3
3
H4), 7.74 (m, 1H, H5), 7.80 (m, 2H, H8), 8.18 (m, 1H, H6), 8.58 H27/26), 3.56 (dh, 2H, JHH 6.8, JPH 17.3 Hz, H25), 6.99 (m,
1
3
3
(m, 1H, H3). C NMR (CDCl , 125.76 MHz) δ 23.10 (d, JPC 2H, H21), 7.04 (m, 2H, H15), 7.18 (m, 2H, H14), 7.25 (m, 1H,
3
3
2
2
4
1
.6 Hz, C27/26), 23.42 (d, JPC 2.9 Hz, C26/27), 47.66 (d, JPC H22), 7.28 (m, 2H, H20), 7.29 (m, 1H, H16), 7.33 (m, 1H, H3),
.1 Hz, C25), 127.26 (d,
2.4 Hz, C21), 127.50 (d, JPC 12.7 Hz, C9), 130.38 (d, JPC 1H, H4), 7.91 (m, 1H, H5), 8.37 (m, 1H, H6) ppm. C NMR
3
.8 Hz, C22), 130.65 (d, JPC 2.8 Hz, C16), 130.69 (dd, JPC 11.0, (CDCl , 125.76 MHz) δ 22.98 (d, JPC 1.5 Hz, C26/27), 23.30 (d,
3
3
J
PC 12.9 Hz, C15), 127.47 (d,
JPC 7.39 (m, 2H, H9), 7.53 (m, 1H, H10), 7.57 (m, 2H, H8), 7.64 (m,
3
4
13
4
3
3
2
4
4
3
3
2
1
JPC 2.6 Hz, C5), 130.83 (d, JPC 2.8 Hz, C10), 131.03 (dd, JPC
JPC 2.7 Hz, C27/26), 48.10 (d, JPC 4.4 Hz, C25), 126.49 (d, JPC
4
2
3
3
1
1.0, J 2.5 Hz, C4), 131.61 (d, J 10.2 Hz, C14), 132.29 (d, 108.1 Hz, C13), 127.88 (d, J 13.3 Hz, C21), 128.28 (d, J
PC PC PC PC
2
2
1
1
3
JPC 9.7 Hz, C20), 132.42 (d, JPC 9.8 Hz, C8), 132.86 (d, JPC 13.0 Hz, C15), 128.36 (d, JPC 126.7 Hz, C19), 128.65 (d, JPC
1
2
1
2
1
23.4 Hz, C19), 134.07 (d, JPC 111.4 Hz, C7), 134.22 (t, JPC
JPC 9.3 Hz, C6), 134.34 (d, J 111.7 Hz, C13), 136.11 (dd, J
6.4, JPC 12.0 Hz, C2), 137.23 (dd, JPC 9.1, JPC 10.9 Hz, C3), 11.0 Hz, C20), 132.26 (d, JPC 2.9 Hz, C22), 132.4 (dd, JPC 11.4,
38.0 (dd, JPC 127.6, JPC 9.2 Hz, C1) ppm. P NMR (CDCl
21.49 MHz) δ 28.91 (d, JPP 5.4 Hz, NPvO), 33.36 (d, JPP 10.5 Hz, C8), 132.8 (d, J 2.8 Hz, C10), 133.73 (dd, J 13.3,
.4 Hz, PvO) ppm. IR (KBr) ν 1157 (PvO, s), 1215 (NPvO, s)
=
12.9 Hz, C9), 129.87 (d, JPC 115.3 Hz, C7), 131.11 (d, JPC 10.6
3
1
1
3
4
2
Hz, C14), 132.02 (dd, J 12.7, J 2.7 Hz, C4), 132.15 (d, J
PC PC PC
PC
PC
2
2
3
4
3
9
1
1
5
1
2
31
4
4
2
3
,
JPC 2.7 Hz, C5), 132.58 (d, JPC 3.1 Hz, C16), 132.66 (d, JPC
3
3
4
2
PC
PC
1
1
2
J
PC 97.9 Hz, C2), 135.89 (dd,
JPC 127.5,
J
PC 9.5 Hz, C1),
−
1
+
2
3
2
3
cm . HRMS (ESI) calcd for C30
found: 502.2066.
2 2 PC PC
H34NO P : 502.2065 (MH ), 136.02 (t, J = JPC 9.7 Hz, C6), 137.71 (dd, JPC 11.8, J
3
1
14.7 Hz, C3) ppm. P NMR (CDCl , 121.49 MHz) δ 37.47 (d,
3
3
3
Compound 20b. Yield 85%. White solid. Mp: 177–178 °C.
J
PP 8.2 Hz, NPvO), 41.27 (d, JPP 8.2 Hz, PvO) ppm. IR (KBr)
1
3
−1
3
H-NMR (CDCl , 500.13 MHz) δ 1.05 (d, 6H, JHH 6.8 Hz, H26/ ν 1118 (PvO, s), 1175 (NPvO, s) cm . HRMS (ESI) calcd for
7), 1.13 (d, 6H, J 6.8 Hz, H27/H26), 3.42 (dh, 2H, J 6.8, C H ClNO P Zn: 600.0967 (M − Cl), found: 600.0978.
3
3
+
2
HH
HH
30 33
2 2
3
JPH 14.9 Hz, H25), 7.13 (m, 2H, H15), 7.2 (m, 2H, H21), 7.23
Complex 21b. Yield after recrystallization 51% (34 mg).
1
(m, 1H, H16), 7.26 (m, 2H, H9), 7.34 (m, 1H, H22), 7.36 (m, White solid. Mp: 273–275 °C, H-NMR (CDCl , 500.13 MHz)
3
3
3
1
H, H10), 7.38 (m, 2H, H20), 7.57 (m, 1H, H4), 7.58 (m, 2H, δ 1.09 (d, 6H, JHH 6.8 Hz, H26/27), 1.28 (d, 6H, J
6.8 Hz,
HH
3
3
H14), 7.7 (m, 1H, H5), 7.71 (m, 2H, H8), 8.18 (bm, 1H, H3), H27/H26), 3.61 (dh, 2H, JHH 6.8, JPH 16.1 Hz, H25), 6.98 (m,
8
1
3
.23 (m, 1H, H6) ppm. C NMR (CDCl
3
, 125.76 MHz) δ 22.96 2H, H15), 7.21 (m, 2H, H21), 7.27 (m, 1H, H16), 7.30 (m, 1H,
3
3
(d, J 2.8 Hz, C27/C26), 23.47 (d, J 2.6 Hz, C26/C27), 47.65 H3), 7.36 (m, 2H, H20), 7.42 (m, 4H, H8 and H14), 7.43 (m,
PC
PC
2
3
(d, JPC 4.0 Hz, C25), 127.44 (d, JPC 12.7 Hz, C15 and C21), 1H, H22), 7.45 (m, 2H, H9), 7.55 (m, 1H, H10), 7.59 (m, 1H,
3
4
13
1
3
27.56 (d, JPC 13.0 Hz, C9), 129.97 (d, JPC 3.1 Hz, C16), 130.15 H4), 7.86 (m, 1H, H5), 8.43 (m, 1H, H6) ppm. C NMR (CDCl ,
4
3
4
3
3
(d, J 3.1 Hz, C10), 130.22 (dd, J 11.1, J 2.9 Hz, C5), 125.76 MHz) δ 23.12 (d,
J
2.2 Hz, C26/27), 24.1 (d, JPC
PC
PC
PC
PC
4
3
4
2
1
1
30.7 (d, JPC 2.7 Hz, C22), 130.78 (dd, JPC 12.5, JPC 2.5 Hz, 2.8 Hz, C27/26), 48.7 (d,
J
PC 3.6 Hz, C25), 124.6 (d,
J
PC
J
PC
PC
2
2
3
3
3
C4), 131.48 (d, JPC 10.5 Hz, C14), 131.85 (d, JPC 10.6 Hz, C8), 86.0 Hz, C13), 128.16 (d,
1
1
JPC 13.6 Hz, C15), 128.49 (d,
2
1
1
32.65 (d,
J
9.6 Hz, C20), 133.02 (d, JPC 122.4 Hz, C19), 13.4 Hz, C21), 128.96 (d, J 130.9 Hz, C19), 129.02 (d, J
PC
PC
2
3
1
1
3
34.87 (dd, JPC 8.9, JPC 9.4 Hz, C6), 135.07 (d, JPC 90.3 Hz, 12.7 Hz, C9), 130.93 (d, JPC 90.8 Hz, C7), 131.64 (dd, JPC 11.3,
1
2
1
4
3
4
C7), 135.7 (d,
J
PC 89.9 Hz, C13), 136.97 (dd,
J
PC 11.1,
J
PC
J
PC 2.9 Hz, C5), 132.3 (dd, JPC 12.7, JPC 3.5 Hz, C4), 132.39
2
3
4
4
7
9.3 Hz, C2), 137.22 (dd, J 13.4, J 11.4 Hz, C3), 137.51 (dd, (d, J 3.1 Hz, C10), 132.41 (d, J 2.9 Hz, C22), 132.54 (d,
PC
PC
PC
PC
2
1
31
2
2
1
2
JPC 9.1, JPC 127.5 Hz, C1) ppm. P NMR (CDCl
3
, 202.45 MHz)
J
J
PC 11.3 Hz, C8), 132.72 (d, JPC 10.7 Hz, C14/C20), 132.75 (d,
3
3
4
δ 28.11 (d, JPP 4.5 Hz, PvO), 50.07 (d, JPP 4.5 Hz, PvS) ppm.
IR (KBr) ν 605 (PvS, s), 1215 (NPvO, s) cm . HR-MS (ESI)
calcd for C30
PC 9.8 Hz, C20/C14), 132.95 (d, JPC 3.3 Hz, C16), 135.24 (dd,
JPC 133.4, J 9.7 Hz, C1), 135.65 (dd, J 80.7, J 12.7 Hz,
PC PC PC
PC 9.7 Hz, C6), 138.04 (t, J = J
PC PC
1.8 Hz, C3) ppm. P NMR (CDCl
JPP 5.2 Hz, PvO), 48.76 (d,
PvS, s), 1125 (NPvO, s) cm . HRMS (ESI) calcd for
−
1
2
1
2
+
2
3
2
3
H
34NOP
2
S: 518.1836 (MH ), found: 518.1838.
C2), 137.11 (t,
J
PC
=
J
3
1
1
3
, 202.45 MHz) δ 34.53 (d,
5.2 Hz, PvS). IR ν 533
3
3
J
PP
−1
General procedure for the synthesis of complexes (21)
(
C
+
To a solution containing 0.10 mmol of the appropriate ligand
30
H
33ClNOP
2
SZn: 616.0738 (M − Cl), found: 616.0741.
2
0a–c in 5 mL of a mixture dichloromethane–acetonitrile (1 : 1)
Complex 21c. Yield after recrystallization 70% (43 mg). Pale
1
2 3
was added 0.10 mmol of ZnCl (0.1 mL of a 1.0 M solution in brown solid. Mp: 273–275 °C. H NMR (CDCl , 500.13 MHz)
diethyl ether) and the reaction was stirred at room temperature δ 1.09 (d, 6H, JHH 6.8 Hz, H26/27), 1.31 (d, 6H, JHH 6.8 Hz,
overnight. Then, the solvent was evaporated under reduced H27/H26), 3.60 (dh, 2H, J
pressure affording pale yellow powders. The P-NMR spectra 2H, H15), 7.23 (m, 5H, H3, H10 and H21), 7.28 (m, 1H, H16),
of the solids obtained showed that complexes 21a–c were 7.40 (m, 2H, H14), 7.42 (m, 2H, H20), 7.44 (m, 2H, H9), 7.45
formed quantitatively. Crystals suitable for X-ray analysis were (m, 1H, H22), 7.53 (m, 2H, H8), 7.58 (m, 1H, H4), 7.86 (m, 1H,
obtained by slow vapour diffusion of diethyl ether into a solu- H5), 8.44 (m, 1H, H6) ppm. C NMR (CDCl
tion containing the complex in dichloromethane–acetonitrile δ 23.18 (d, JPC 2.7 Hz, C26/27), 24.02 (d, JPC 3.1 Hz, C27/26),
3
3
3
3
6.8, J 15.6 Hz, H25), 6.99 (m,
PH
HH
3
1
1
3
3
, 125.76 MHz)
3
3
2
1
(1 : 1).
48.85 (d, J 3.4 Hz, C25), 123.23 (d, J 79.1 Hz, C13), 128.35
PC PC
This journal is © The Royal Society of Chemistry 2014
Dalton Trans., 2014, 43, 14079–14091 | 14087