Full Paper
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arom. CH, resorcin.), 7.56 (s, 1 H, arom. CH, resorcin.), 7.27–7.23 (m,
4 H, arom. CH, PPh2), 7.02–6.94 (m, 3 H, arom. CH, C6H4 and PPh2),
6.89 (t, 3J = 6.5 Hz, 4 H, arom. CH, PPh2), 6.80 (s, 2 H, arom. CH,
CHCH2), 1.48–1.37 (m, 24 H, CH2CH2CH2CH3), 0.98 (t, J = 7.0 Hz, 6
H, CH2CH3), 0.96 (t, 3J = 7.0 Hz, 6 H, CH2CH3) ppm. 13C NMR
(126 MHz, CDCl3): δ = 155.07 (s, arom. CqO), 154.93 (s, arom. CqO),
resorcin.), 6.80–6.78 (m, 2 H, arom. CH, C6H4), 6.16 (s, 1 H, arom. CH, 154.64 (s, arom. CqO), 152.49 (s, arom. CqO), 140.84–116.01 (arom.
2
resorcin.), 5.60 and 4.42 (AB spin system, J = 7.0 Hz, 4 H, OCH2O),
Cs), 99.81 (s, OCH2O), 99.30 (s, OCH2O), 36.62 (s, CHCH2), 36.52 (s,
CHCH2), 32.24 (s, CH2CH2CH3), 32.20 (s, CH2CH2CH3), 30.09 (s,
4.16 (t, 3J = 8.0 Hz, 2 H, CHCH2), 5.12–5.09 (m, 2 H, CHCH2), 5.01
and 4.24 (AB spin system, J = 7.0 Hz, 4 H, OCH2O), 4.87–4.84 (m, 1 CHCH2), 29.94 (s, CHCH2), 27.74 (s, CHCH2CH2), 22.93 (s, CH2CH3),
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H, arom. CH, C6H4), 2.86–2.79 (m, 2 H, CHCH2), 2.68–2.60 (m, 2 H,
CHCH2), 2.42–2.34 (m, 2 H, CHCH2), 2.29–2.23 (m, 2 H, CHCH2), 1.60–
1.19 (m, 24 H, CH2CH2CH2CH3), 0.90 (t, 3J = 7.0 Hz, 6 H, CH2CH3),
0.82 (t, 3J = 7.2 Hz, 6 H, CH2CH3) ppm. 13C NMR (126 MHz, C6D6):
δ = 155.88 (s, arom. CqO), 155.56 (s, arom. CqO), 155.40 (s, arom.
CqO), 152.20 (s, arom. CqO), 140.25–116.83 (arom. Cs), 99.34 (s,
OCH2O), 99.59 (s, OCH2O), 37.38 (s, CHCH2), 37.05 (s, CHCH2), 32.46
(s, CH2CH2CH3), 32.33 (s, CH2CH2CH3), 30.45 (s, CHCH2), 30.06 (s,
CHCH2), 28.12 (s, CHCH2CH2), 28.05 (s, CHCH2CH2), 23.23 (s, CH2CH3),
23.09 (s, CH2CH3), 14.49 (s, CH2CH3), 14.31 (s, CH2CH3) ppm. 31P{1H}
NMR (162 MHz, C6D6): δ = 24.4 [s, P(O)Ph2] ppm. MS (ESI-TOF):
m/z = 1093.53 [M + H]+; expected isotopic profiles. C70H77O9P
(1093.33): calcd. C 76.90, H 7.10; found C 77.02, H 7.22.
22.86 (s, CH2CH3), 14.33 (s, CH2CH3), 14.27 (s, CH2CH3) ppm. 31P{1H}
NMR (162 MHz, CDCl3): δ = –10.5 (s, PPh2) ppm. C70H77O8P
(1077.33): calcd. C 78.04, H 7.20; found C 78.09, H 7.25.
5-(2-Dicyclohexylphosphinophenyl)-4(24),6(10),12(16),18(22)-
tetramethylenedioxy-2,8,14,20-tetrapentylresorcin[4]arene (2):
Yield: 1.388 g, 88 %. 1H NMR (400 MHz, CDCl3): δ = 7.56 (d, 3J =
7.6 Hz, 1 H, arom. CH, C6H4), 7.30 (t, 3J = 7.2 Hz, 1 H, arom. CH,
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C6H4), 7.24 (t, J = 7.2 Hz, 1 H, arom. CH, C6H4), 7.21 (s, 1 H, arom.
CH, resorcin.), 7.19 (s, 2 H, arom. CH, resorcin.), 7.15 (s, 1 H, arom.
3
4
CH, resorcin.), 6.77 (dd, J = 6.4, J = 2.0 Hz, 1 H, C6H4), 6.52 (s, 1 H,
arom. CH, resorcin.), 6.45 (s, 2 H, arom. CH, resorcin.), 5.79 and 4.45
(AB spin system, 2J = 7.2 Hz, 4 H, OCH2O), 5.25 and 4.34 (AB spin
2
3
system, J = 7.2 Hz, 4 H, OCH2O), 4.77 (t, J = 7.6 Hz, 2 H, CHCH2),
4.76 (t, 3J = 8.0 Hz, 2 H, CHCH2), 2.37–2.25 (m, 8 H, CHCH2), 1.80–
1.62 (m, 10 H, PCy2), 1.51–1.36 (m, 26 H, CH2CH2CH2CH3 and PCy2),
5-(2-Dicyclohexylphosphinoylphenyl)-4(24),6(10),12(16),18(22)-
tetramethylenedioxy-2,8,14,20-tetrapentylresorcin[4]arene (8):
Yield: 0.683 g, 60 %. Rf = 0.32 (CH2Cl2/Et2O, 9:1, v/v). 1H NMR
(500 MHz, CDCl3): δ = 8.28–8.24 (m, 1 H, arom. CH, C6H4), 7.45 (t,
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1.27–1.11 (m, 10 H, PCy2), 0.94 (t, J = 7.0 Hz, 12 H, CH2CH3) ppm.
13C NMR (100 MHz, CDCl3): δ = 155.13 (s, arom. CqO), 155.00 (s,
arom. CqO), 154.67 (s, arom. CqO), 152.54 (s, arom. CqO), 138.90–
116.22 (arom. Cs), 99.84 (s, OCH2O), 99.30 (s, OCH2O), 36.58 (s,
3J = 7.5 Hz, 1 H, C6H4), 7.36 (t, J = 7.2 Hz, 1 H, C6H4), 7.23 (s, 1 H,
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arom. CH, resorcin.), 7.19 (s, 1 H, arom. CH, resorcin.), 7.16 (s, 2 H,
arom. CH, resorcin.), 6.79–6.77 (m, 1 H, arom. CH, C6H4), 6.52 (s, 1
H, arom. CH, resorcin.), 6.45 (s, 2 H, arom. CH, resorcin.), 5.79 and
4.40 (AB spin system, 2J = 7.0 Hz, 4 H, OCH2O), 5.22 and 4.34 (AB
spin system, 2J = 7.0 Hz, 4 H, OCH2O), 4.76 (t, 3J = 8.5 Hz, 2 H,
CHCH2), 4.74 (t, 3J = 8.5 Hz, 2 H, CHCH2), 2.35–2.20 (m, 8 H, CHCH2),
1.94–1.81 (m, 2 H, PCy2), 1.75–1.73 (m, 4 H, PCy2), 1.69–1.65 (m, 2
H, PCy2 ), 1.60–1.52 (m, 4 H, PCy2 ), 1.48–1.34 (m, 26 H,
CH2CH2CH2CH3 and PCy2), 1.29–1.15 (m, 6 H, PCy2), 1.10–1.03 (m, 2
H, PCy2), 0.93 (t, J = 7.2 Hz, 6 H, CH2CH3), 0.93 (t, J = 7.2 Hz, 6 H,
CH2CH3) ppm. 13C NMR (126 MHz, CDCl3): δ = 155.03 (s, arom. CqO),
154.87 (s, arom. CqO), 154.83 (s, arom. CqO), 153.05 (s, arom. CqO),
138.82–116.01 (arom. Cs), 99.85 (s, OCH2O), 99.20 (s, OCH2O), 38.02
(d, JPC = 65.8 Hz, PCH), 36.76 (s, CHCH2), 36.54 (s, CHCH2), 32.16 (s,
CH2CH2CH3), 32.06 (s, CH2CH2CH3), 30.23 (s, CHCH2), 29.90 (s,
CHCH2), 27.90 (s, CHCH2CH2), 27.70 (s, CHCH2CH2), 27.01 (d, JPC
12.6 Hz, PCHCH2), 26.61 (d, JPC = 26.6 Hz, PCHCH2CH2), 25.86 (s,
PCHCH2CH2CH2), 22.84 (s, CH2CH3), 22.82 (s, CH2CH3), 14.27 (s,
CH2CH3), 14.21 (s, CH2CH3) ppm. 31P{1H} NMR (162 MHz, CDCl3): δ =
47.7 [s, P(O)Cy2] ppm. C70H89O9P (1105.43): calcd. C 76.06, H 8.11;
found C 76.21, H 8.19.
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CHCH2), 34.46 (d, JPC = 15.1 Hz, PCH), 32.21 (s, CH2CH2CH3), 32.00
(s, CH2CH2CH3), 30.31 (d, JPC = 17.4 Hz, PCHCH2), 30.04 (s, CHCH2),
30.01 (s, CHCH2), 29.47 (d, JPC = 9.7 Hz, PCHCH2CH2), 27.75 (s,
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CHCH2CH2), 27.61 (s, CHCH2CH2), 26.65 (s, PCHCH2CH2CH2), 22.87 (s,
CH2CH3), 22.85 (s, CH2CH3), 14.24 (s, CH2CH3) ppm. 31P{1H} NMR
(162 MHz, CDCl3): δ = –8.7 (s, PCy2) ppm. C70H89O8P (1089.43): calcd.
C 77.17, H 8.23; found C 77.15, H 8.21.
Bis{chlorido(μ-chlorido)[5-(2-diphenylphosphinophenyl)-
4(24),6(10),12(16),18(22)-tetramethylenedioxy-2,8,14,20-
tetrapentylresorcin[4]arene]palladium(II)} (9): A solution of
[PdCl2(PhCN)2] (0.037 g, 0.09 mmol) in CH2Cl2 (10 mL) was added
to a stirred solution of 1 (0.050 g, 0.05 mmol) in CH2Cl2 (10 mL).
After stirring for 0.5 h, the reaction mixture was concentrated to
about 1 mL and MeOH (20 mL) was added. The yellow precipitate
was separated by filtration and dried under vacuum. Slow diffusion
of MeOH (10 mL) into a solution of the crude product in CHCl3
(3 mL) led to the formation of orange crystals, which were sepa-
rated by filtration and dried under vacuum to afford complex 9
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3
1
2
=
3
1
(0.030 g, 51 % yield, based on the amount of isolated crystals). H
NMR (500 MHz, CDCl3): δ = 7.91–7.87 (m, 8 H, arom. CH, PPh2),
7.81–7.76 (m, 2 H, arom. CH, C6H4), 7.33–7.28 (m, 8 H, arom. CH,
PPh2 and C6H4), 7.20 (t, J = 6.7 Hz, 8 H, arom. CH, PPh2), 7.14 (s, 2
General Procedure for the Preparation of Phosphines 1 and 2:
A suspension of phosphine 7 or 8 oxide in PhSiH3 (10 equiv./phos-
phine oxide) was stirred for 24 h at 110 °C. The reaction mixture
was cooled to room temperature and then the solution was evapo-
rated to dryness. The residue was washed with MeOH (3 × 10 mL)
to afford the phosphine as a white solid.
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H, arom. CH, resorcin.), 7.05 (s, 4 H, arom. CH, resorcin.), 6.81 (s, 2
H, arom. CH, resorcin.), 6.69–6.66 (m, 2 H, arom. CH, C6H4), 6.49 (s,
2 H, arom. CH, resorcin.), 6.41 (s, 4 H, arom. CH, resorcin.), 5.76 and
4.37 (AB spin system, 2J = 7.5 Hz, 8 H, OCH2O), 5.47 and 4.23 (AB
spin system, 2J = 7.0 Hz, 8 H, OCH2O), 4.72 (t, 3J = 8.0 Hz, 4 H,
CHCH2), 4.56–4.53 (m, 4 H, CHCH2), 2.35–2.17 (m, 12 H, CHCH2),
1.95–1.88 (m, 4 H, CHCH2), 1.48–1.33 (m, 48 H, CH2CH2CH2CH3), 0.95
5-(2-Diphenylphosphinophenyl)-4(24),6(10),12(16),18(22)-
tetramethylenedioxy-2,8,14,20-tetrapentylresorcin[4]arene (1):
Yield: 0.409 g, 83 %. 1H NMR (500 MHz, CDCl3): δ = 7.30–7.25 (m, (t, 3J = 7.0 Hz, 12 H, CH2CH3), 0.92 (t, 3J = 7.5 Hz, 12 H, CH2CH3) ppm.
12 H, arom. CH, PPh2 and C6H4), 7.21 (s, 1 H, arom. CH, resorcin.),
13C NMR (126 MHz, CDCl3): δ = 155.37 (s, arom. CqO), 154.94 (s,
7.16 (s, 2 H, arom. CH, resorcin.), 7.14–7.12 (m, 1 H, arom. CH, C6H4), arom. CqO), 154.72 (s, arom. CqO), 151.52 (s, arom. CqO), 139.00–
7.08 (s, 1 H, arom. CH, resorcin.), 6.83–6.80 (m, 1 H, arom. CH, C6H4), 115.75 (arom. Cs), 99.87 (s, OCH2O), 99.03 (s, OCH2O), 36.51 (s,
6.53 (s, 1 H, arom. CH, resorcin.), 6.47 (s, 2 H, arom. CH, resorcin.),
CHCH2), 32.39 (s, CH2CH2CH3), 32.23 (s, CH2CH2CH3), 30.20 (s,
CHCH2), 30.00 (s, CHCH2), 29.86 (s, CHCH2), 27.87 (s, CHCH2CH2),
27.78 (s, CHCH2CH2), 22.95 (s, CH2CH3), 22.89 (s, CH2CH3), 14.40 (s,
CH2CH3), 14.28 (s, CH2CH3) ppm. 31P{1H} NMR (162 MHz, CDCl3): δ =
5.81 and 4.45 (AB spin system, 2J = 7.0 Hz, 4 H, OCH2O), 5.31 and
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4.36 (AB spin system, J = 7.0 Hz, 4 H, OCH2O), 4.78 (t, J = 8.0 Hz,
2 H, CHCH2), 4.60 (t, 3J = 7.7 Hz, 2 H, CHCH2), 2.30–2.17 (m, 8 H,
Eur. J. Inorg. Chem. 2017, 685–693
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© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim