I. Fernández, M. A. Sierra, M. J. Mancheño, M. Gómez-Gallego, F. P. Cossío
FULL PAPER
133.0 (d, JC,P = 11.2 Hz), 133.5 (d, JC,P = 6.9 Hz), 134.0 (d, JC,P
18.6 Hz), 136.0 (d, JC,P = 34.5 Hz), 140.0 (d, JC,P = 14.1 Hz), 222.4
(d, JC,P = 7.4 Hz), 228.4 (d, JC,P = 1.8 Hz), 229.9 (d, JC,P
=
2.16 (s, 3 H), 2.21 (m, 2 H), 2.50 (m, 2 H), 3.28 (q, J = 7.0 Hz, 1 H),
3.60 (s, 3 H), 7.38–7.71 (m, 10 H, ArH) ppm. 13C NMR (75.5 MHz,
CDCl3): δ = 14.4, 19.7 (d, JC,P = 3.3 Hz), 27.0 (d, JC,P = 73.1 Hz),
37.5, 51.1, 54.2 (d, JC,P = 15.4 Hz), 61.1, 128.5 (d, JC,P = 11.5 Hz),
=
16.4 Hz), 282.9 (d, JC,P = 12.6 Hz) ppm. IR (KBr): ν = 1994, 1913,
˜
1871, 1840 cm–1. C32H26CrNO4P (571.52): calcd. C 67.25, H 4.59,
N 2.45; found C 67.01, H 4.43, N 2.34.
130.7 (d, JC,P = 9.2 Hz), 131.6 (d, JC,P = 2.6 Hz), 133.0 (d, JC,P =
98.3 Hz), 173.6 ppm. 31P NMR (121, MHz, CDCl3): δ = 34.1 ppm.
IR (CCl ): ν = 1936, 1732, 1437, 1215 cm–1. ESI-MS: m/z = 359.
1
˜
4
7e: 258 mg (99%), yellow solid. H NMR (300 MHz, CDCl3): δ =
C20H26NO3P (359.40): calcd. C 66.84, H 7.29, N 3.90; found C
66.67, H 7.05.
2.74 (s, 3 H), 4.20 (br. s, 2 H), 5.11 (br. s, 1 H), 5.25 (d, J = 10.2 Hz,
2 H), 5.72 (m, 1 H), 5.94 (br. s, 1 H), 6.90 (m, 1 H, ArH), 7.26–
7.54 (m, 13 H, ArH) ppm. 13C NMR (75.5 MHz, CDCl3): δ = 39.5
(d, JC,P = 4.1 Hz), 54.4, 62.9 (d, JC,P = 12.1 Hz), 117.8, 128.2 (d,
JC,P = 9.0 Hz), 129.5, 129.6, 130.1 (d, JC,P = 6.3 Hz), 130.3, 132.9
(m), 133.6, 133.8 (d, JC,P = 18.5 Hz), 136.1 (d, JC,P = 34.2 Hz),
140.1 (d, JC,P = 14.2 Hz), 222.4 (d, JC,P = 10.6 Hz), 228.4 (d, JC,P
= 1.7 Hz), 229.8 (d, JC,P = 16.4 Hz), 282.0 (d, JC,P = 12.8 Hz) ppm.
9c: 80 mg (41%), yellow solid. 1H NMR (300 MHz, CDCl3): δ =
0.84 (d, J = 7.1 Hz, 3 H), 2.00 (s, 3 H), 3.32 (q, J = 7.1 Hz, 1 H),
3.59 (s, 3 H), 3.83 (qd, J1 = 6.0, J2 = 1.7 Hz, 2 H), 6.86 (m, 1 H,
ArH), 7.10–7.37 (m, 13 H, ArH) ppm. 13C NMR (75.5 MHz,
CDCl3): δ = 14.4, 35.5, 51.0, 58.2 (d, JC,P = 18.2 Hz), 59.7, 127.2,
128.1, 128.3 (d, JC,P = 10.3 Hz), 128.3 (d, JC,P = 6.9 Hz), 128.6,
IR (KBr): ν = 1996, 1894, 1875, 1846 cm–1. C H CrNO P
˜
28 24
4
129.3 (d, JC,P = 5.7 Hz), 133.4 (d, JC,P = 19.3 Hz), 133.7 (d, JC,P
22.3 Hz), 134.4, 136.7 (d, JC,P = 15.5 Hz), 137.8 (d, JC,P = 10.3 Hz),
137.9 (d, JC,P = 10.0 Hz), 144.2 (d, JC,P = 23.6 Hz), 173.9 ppm. 31
=
(521.46): calcd. C 64.49, H 4.64, N 2.69; found C 64.61, H 4.73.
P
General Procedure for the Photochemical Reactions of Complexes 7:
Photochemical reactions were conducted by using a 450 W me-
dium-pressure Hg lamp, through a Pyrex filter in dry degassed
CH3CN or CH3CN/thf containing CH3OH in a sealed Pyrex tube
filled with argon. In a typical experiment, after irradiation for 30 h,
the solution was filtered through a short pad of Celite, the solvent
was removed under reduced pressure, and the crude product was
submitted to flash chromatography to give pure complexes 8 and
9.
NMR (121, MHz, CDCl ): δ = –12.6 ppm. IR (CCl ): ν = 1942,
˜
3
4
1736, 1433 cm–1. C24H26NO2P (391.44): calcd. C 73.64, H 6.69, N
3.58; found C 73.89, H 6.48.
1
9d: 140 mg (60%), pale yellow oil. H NMR (300 MHz, CDCl3): δ
= 1.14 (d, J = 7.1 Hz, 3 H), 3.38 (q, J = 7.1 Hz, 1 H), 3.56 (s, 3
H), 3.58 (q, J = 14.1 Hz, 2 H), 3.87 (qd, J1 = 17.8, J2 = 3.3 Hz, 2
H), 6.73 (m, 1 H, ArH), 7.04–7.29 (m, 17 H, ArH), 7.68 (m, 1 H,
ArH) ppm. 13C NMR (75.5 MHz, CDCl3): δ = 14.3, 51.2, 52.1 (d,
JC,P = 24.6 Hz), 54.4, 56.5, 126.8 (d, JC,P = 9.2 Hz), 128.1, 128.4,
128.5 (d, JC,P = 3.5 Hz), 128.6 (d, JC,P = 6.6 Hz), 128.7, 128.8 (d,
1
8a: 199 mg (98%), yellow solid. H NMR (300 MHz, CDCl3): δ =
2.03 (m, 1 H), 2.22 (m, 1 H), 2.58 (d, J = 4.1 Hz, 3 H), 2.69 (m, 1
H), 2.69 (m, 1 H), 2.96 (m, 1 H), 7.31–7.60 (m, 10 H, ArH) ppm.
13C NMR (75.5 MHz, CDCl3): δ = 28.1 (d, JC,P = 16.1 Hz), 46.1,
JC,P = 11.5 Hz), 133.1, 133.7 (d, JC,P = 3.5 Hz), 134.0 (d, JC,P
=
3.2 Hz), 136.0 (d, JC,P = 14.5 Hz), 136.5 (d, JC,P = 10.6 Hz), 136.8
(d, JC,P = 10.5 Hz), 139.7, 144.0 (d, JC,P = 22.2 Hz), 174.2 ppm.
54.0 (d, JC,P = 11.8 Hz), 128.7 (d, JC,P = 9.3 Hz), 128.8 (d, JC,P
=
31P NMR (121, MHz, CDCl ): δ = –14.8 ppm. IR (CCl ): ν = 1942,
9.1 Hz), 129.9 (d, JC,P = 1.6 Hz), 130.0 (d, JC,P = 1.7 Hz), 131.1 (d,
JC,P = 11.7 Hz), 131.6 (d, JC,P = 11.8 Hz), 135.7 (d, JC,P = 17.6 Hz),
136.2 (d, JC,P = 14.6 Hz), 218.1 (d, JC,P = 13.7 Hz), 218.4 (d, JC,P
= 14.1 Hz), 226.6 (d, JC,P = 2.6 Hz), 228.0 (d, JC,P = 12.8 Hz) ppm.
˜
3
4
1736, 1433 cm–1. C30H30NO2P (467.54): calcd. C 77.07, H 6.47, N
3.00; found C 76.89, H 6.66.
1
9e: 115 mg (55%), pale yellow oil. H NMR (300 MHz, CDCl3): δ
IR (CCl ): ν = 2012, 1954, 1888 cm–1. C H CrNO P (407.32):
˜
4
19 18
4
= 1.02 (d, J = 7.1 Hz, 3 H), 3.03 (qd, J1 = 13.6, J2 = 5.6 Hz, 2 H),
3.38 (q, J = 7.1 Hz, 1 H), 3.54 (s, 3 H), 3.88 (qd, J1 = 15.9, J2 =
2.2 Hz, 2 H), 4.93 (d, J = 10.1 Hz, 1 H), 5.02 (dd, J1 = 17.2, J2 =
1.5 Hz, 1 H), 5.60 (m, 1 H), 6.78 (m, 1 H, ArH), 7.06–7.27 (m, 12
H, ArH), 7.55 (m, 1 H, ArH) ppm. 13C NMR (75.5 MHz, CDCl3):
δ = 14.5, 51.1, 52.8 (d, JC,P = 22.4 Hz), 53.4, 57.0, 116.8, 126.9,
128.3, 128.4, 128.5 (d, JC,P = 3.2 Hz), 128.9 (d, JC,P = 5.4 Hz),
133.6, 133.7 (d, JC,P = 10.9 Hz), 133.9 (d, JC,P = 9.8 Hz), 136.0 (d,
calcd. C 56.03, H 4.45, N 3.44; found C 56.28, H 4.59.
8c: 82 mg (35%), yellow solid. 1H NMR (300 MHz, CDCl3): δ =
2.41 (d, J = 6.3 Hz, 3 H), 2.98 (br. s, 1 H), 3.43 (m, 2 H), 6.74 (m,
1 H, ArH), 7.28–7.42 (m, 13 H, ArH) ppm. 13C NMR (75.5 MHz,
CDCl3): δ = 46.1, 60.7 (d, JC,P = 12.7 Hz), 128.5 (d, JC,P = 1.8 Hz),
128.7 (d, JC,P = 2.0 Hz), 129.9, 130.2 (d, JC,P = 13.6 Hz), 131.1 (d,
JC,P = 22.6 Hz), 131.5, 132.0 (d, JC,P = 7.4 Hz), 132.9 (d, JC,P
=
11.5 Hz), 134.1 (d, JC,P = 34.8 Hz), 138.7 (d, JC,P = 17.1 Hz), 218.2
(d, JC,P = 13.1 Hz), 218.8 (d, JC,P = 13.1 Hz), 225.1, 226.2 (d, JC,P
JC,P = 14.7 Hz), 136.6, 136.9 (d, JC,P = 10.2 Hz), 137.3 (d, JC,P
=
10.9 Hz), 144.3 (d, JC,P = 22.8 Hz), 174.3 ppm. 31P NMR (121,
= 13.6 Hz) ppm. IR (KBr): ν = 3288, 2004, 1878, 1838 cm–1.
˜
MHz, CDCl3): δ = –13.4 ppm. IR (CCl ): ν = 1942, 1736,
˜
4
1433 cm–1. C26H28NO2P (417.48): calcd. C 78.40, H 6.76, N 3.36;
C24H20CrNO4P (469.39): calcd. C 61.41, H 4.29, N 2.98; found C
61.25, H 4.46.
found C 78.55, H 6.58, N 3.55.
1
8d: 87 mg (32%), yellow solid. H NMR (300 MHz, CDCl3): δ =
Supporting Information (see footnote on the first page of this arti-
cle): Cartesian coordinates (in Å), and total energies (in a.u., non-
corrected zero-point vibrational energies included) of all the sta-
tionary points discussed in the text.
3.22–3.45 (m, 4 H), 4.08 (d, J = 13.2 Hz, 1 H), 6.79–6.88 (m, 2 H),
7.11–7.45 (m, 17 H, ArH) ppm. 13C NMR (75.5 MHz, CDCl3): δ
= 54.4 (d, JC,P = 12.0 Hz), 60.8, 128.2, 128.4, 128.5 (d, JC,P
=
5.3 Hz), 128.6 (d, JC,P = 5.5 Hz), 129.1, 129.9 (d, JC,P = 2.7 Hz),
129.9, 130.1, 130.1 (d, JC,P = 5.5 Hz), 131.6, 131.7, 131.9, 132.2 (d,
JC,P = 7.5 Hz), 132.5, 132.8 (d, JC,P = 11.5 Hz), 133.2, 133.4 (d,
JC,P = 36.8 Hz), 133.7 (d, JC,P = 11.6 Hz), 134.2 (d, JC,P = 34.9 Hz),
136.7, 138.5 (d, JC,P = 16.5 Hz), 218.2 (d, JC,P = 12.9 Hz), 219.0
(d, JC,P = 12.9 Hz), 224.8, 226.4 (d, JC,P = 13.4 Hz) ppm. IR (KBr):
Acknowledgments
Support for this work by the Ministerio de Ciencia y Tecnología
(Spain) and the Euskal Herriko Unibertsitatea (9/UPV 00040.215-
13548/2001) (to F. P. C) under the grants CTQ2004-06250-C02-01/
BQU, CTQ2007-67730-C02-01/BQU, CAM-UCM-910762 (to
M. A. S), and CTQ2004-0681/BQU (to F. P. C) are gratefully ac-
ν = 3288, 2004, 1878, 1838 cm–1. C H CrNO P (545.48): calcd.
˜
30 24
4
C 66.06, H 4.43, N 2.57; found C 65.87, H 4.66.
9b: 180 mg (quantitative yield), pale yellow oil. 1H NMR
(300 MHz, CDCl3): δ = 1.17 (d, J = 7.0 Hz, 3 H), 1.17 (m, 2 H),
2460
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Eur. J. Inorg. Chem. 2008, 2454–2462