(Allyl)(arene)nickel(II) and (Allyl)(arene)palladium(II)
Organometallics, Vol. 28, No. 8, 2009 2381
25 °C): δ 7.03 (s, 3H, mesAr), 5.65 (m, 1H, R ) Hc), 4.54 (d, 2H,
4H, H1,1′ or H2,2′), 5.11 (m, 4H, H2,2’ or H1,1′), 5.27 (s, 2H, Hsyn),
4.02 (s, 2H, Hanti). 13C{1H} NMR (100 MHz, CDCl2F, -110 °C):
δ 128.3 (s, C2), 96.4 (s C3), 80.7 (s, C1). Free mesitylene was
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3JH-H ) 4.8 Hz, Hsyn), 3.30 (d, 2H, JH-H ) 11.4 Hz, Hanti), 2.44
(s, 9H, mesCH ). 13C{1H} NMR (100 MHz, CD2Cl2, 0 °C): δ 133.4
(s, mes Cipso),3 116.8 (s, mes CAr), 109.1 (s, C2), 65.7 (s, C1), 20.9
(s, mes CCH ). Anal. Calcd for C12H17F6SbPd: C, 28.63; H, 3.41.
Found: C, 238.60; H, 3.34.
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observed: H NMR (500 MHz CDCl2F, -110 °C) δ 6.73 (s, 3H,
mesAr), 2.14 (s, 9H, mesCH3); 13C{1H} NMR (100 MHz, CDCl2F,
-110 °C) δ 137.9 (s, mes CCH ), 126.9 (s, mes CAr), 21.4 (s, CH3).
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[(2-Methallyl)Pd(mes)][SbF6] (5-Me). [(2-methallyl)PdBr]2 (0.350
g, 0.720 mmol), mesitylene (500 µL, 2.88 mmol), and AgSF6 (0.600
g, 1.44 mmol). Yield: 0.677 g (82%). 1H NMR (400 MHz, CD2Cl2,
25 °C): δ 7.03 (s, 3H, mesAr), 4.32 (s, 2H, Hsyn), 3.10 (s, 2H, Hanti),
Free ethylene was observed: H NMR (500 MHz CDCl2F, -110
°C) δ 5.48 (s, 2H, vinyl); 13C{1H} NMR (100 MHz, CDCl2F, -110
°C) 122.7 (s, C3).
2.44 (s, 9H, mesCH ), 2.08 (s, 3H, R ) CH3). 13C{1H} NMR (100
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MHz, CD2Cl2, 0 °C): δ 133.7 (s, mes Cipso), 126.9 (s, C2), 117.4
(s, mes CAr), 64.6 (s, C1), 21.7 (s, R ) CH3), 20.9 (s, mes CCH ).
Anal. Calcd for C13H19F6SbPd: C, 30.17; H, 3.71. Found: C, 29.939;
H, 3.59.
[(2-Cl-allyl)Pd(mes)][SbF6] (5-Cl). [(2-Cl-allyl)PdCl]2 (0.192
g, 0.440 mmol), mesitylene (240 µL, 1.76 mmol), and AgSbF6
(0.302 g, 0.880 mmol). Yield: 0.393 g (83%). 1H NMR (400 MHz,
CD2Cl2, 25 °C): δ 7.12 (s, 3H, mesAr), 4.72 (s, 2H, Hsyn), 3.57 (s,
2H, Hanti), 2.44 (s, 9H, mesCH ). 13C{1H} NMR (100 MHz, CD2Cl2,
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25 °C): δ 134.0 (s, mes Cipso), 124.9 (s, C2), 117.1 (s, mes CAr),
65.6 (s, C1), 20.9 (s, mes CCH ). Anal. Calcd for C12H16F6SbPd: C,
26.79; H, 3.00. Found: C, 273.70; H, 3.23.
[(Allyl)Pd(C6Me6)][SbF6] (6-H). [(Allyl)PdCl]2 (0.160 g, 0.440
mmol), hexamethylbenzene (0.286 g, 1.76 mmol), and AgSbF6
(0.302 g, 0.880 mmol). Yield: 0.370 g (76%). 1H NMR (400 MHz,
CD2Cl2, 25 °C): δ 5.55 (m, 1H, R ) H), 4.10 (d, 3JH-H ) 6.5, 2H,
In Situ Generation of [(allyl)Pd(cyclopentene)2][SbF6]
(12-H). A screw-cap NMR tube was charged with [(allyl)Pd-
(mes)][SbF6] (5-H; 0.011 g, 0.020 mmol) dissolved in 400 µL of
CD2Cl2. The tube was then placed in a -78 °C bath, and 4 equiv
of cyclopentene (10 µL, 0.080 mmol) was added via syringe. The
tube was inverted quickly to allow mixing, and the solution turned
Hsyn), 3.01 (d, 3JH-H ) 11.5 Hz, 2H, Hanti), 2.50 (s, 18H, hmbCH ).
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13C{1H} NMR (100 MHz, CD2Cl2, 25 °C): δ 126.5 (s, hmb Cipso),
109.1 (s, C2), 64.0 (s, C1), 17.2 (s, hmb CH3). Anal. Calcd for
C15H23F6SbPd: C, 33.02; H, 4.26. Found: C, 33.33; H, 4.31.
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from yellow to colorless. H NMR (500 MHz, CD2Cl2, -60 °C):
δ 6.03 (s, 2H, H1 or H2), 5.80 (s, 2H, H2 or H1), 5.58 (m, 1H, Hc),
5.17 (d, 3JH-H ) 7.0 Hz, 2H, Hsyn), 3.65 (d, 3JH-H ) 13.0 Hz, 2H,
Hanti), 2.51 (bs, 8H, H4,4′ and H3,3′), 1.92 (bs, 2H, H5 or H5′), 1.11
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(m, 2H, H5′ or H5). Free mesitylene was observed: H NMR (500
MHz, CD2Cl2, -60 °C) δ 6.83 (s, 3H, mesAr), 2.26 (s, 9H, mesCH ).
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Free cyclopentene was observed: 1H NMR (500 MHz, CD2Cl2, -60
°C) δ 5.74 (s, 4H, H1,2), 2.30 (bs, 8H, H3,4), 1.81 (m, 4H, H5).
In Situ Generation of [(2-Cl-allyl)Pd(cyclopentene)2][SbF6]
(12-Cl). A screw-cap NMR tube was charged with [(2-Cl-
allyl)Pd(mes)][SbF6] (5-Cl; 0.010 g, 0.019 mmol) dissolved in 500
µL of CD2Cl2. The tube was then placed in a -78 °C bath, and 5
equiv of cyclopentene (10 µL, 0.093 mmol) was added via syringe.
The tube was inverted quickly to allow mixing, and the solution
turned from yellow to colorless. Variable-temperature spectra are
shown in Figure 5. 1H NMR (500 MHz, CD2Cl2, -76 °C): δ 6.16
(s, 2H, H1 or H2), 5.86 (s, 2H, H2 or H1), 5.28 (s, 2H, Hsyn), 3.96
(s, 2H, Hanti), 2.51 (br m, 8H, H4,4′ and H3,3′), 1.92 (br m, 2H, H5
or H5′), 1.05 (m, 2H, H5′ or H5). 13C{1H} NMR (100 MHz, CD2Cl2,
-87 °C): δ 126.8 (C2), 113.7 (C3 or C4), 113.3 (C3 or C4), 83.6
(C1), 35.0 (C5 or C7), 34.8 (C7 or C5), 22.6 (C6). Free mesitylene
Synthesis of (allyl)PdII Bis-Olefin Complexes.
In Situ Generation of [(Allyl)Pd(ethylene)2][SbF6] (10-H). A
J-Young NMR tube was charged with [(allyl)Pd(mes)][SbF6] (5-
H; 0.011 g, 0.020 mmol) dissolved in ca. 400 µL of CDCl2F. The
yellow solution was frozen in liquid nitrogen, and approximately
2 equiv (67.5 mmHg, 0.040 mmol) of ethylene was admitted via a
10.94 mL calibrated gas bulb on a high-vacuum line. The tube was
then moved to a -78 °C dry ice/isopropyl alcohol bath. The tube
was inverted to allow mixing, and the solution turned from yellow
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was observed: H NMR (500 MHz, CD2Cl2, -76 °C) δ 6.79 (s,
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to colorless. H NMR (500 MHz, CDCl2F, -110 °C): δ 5.73 (m,
3H, mesAr), 2.24 (s, 9H, mesCH ); 13C{1H} NMR (100 MHz, CD2Cl2,
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1H, Hc), 5.32 (d, JH-H ) 7.0 Hz, 2H, Hsyn), 5.28 (m, 4H, H1 or
-87 °C) δ 137.7 (s, mes CCH ), 126.8 (s, mes CAr), 21.4 (s, CH3).
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H2), 5.03 (m, 4H, H2 or H1), 3.80 (d, JH-H ) 13 Hz, 2H, Hanti).
Free cyclopentene was observed: 1H NMR (500 MHz, CD2Cl2, -76
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Free mesitylene was observed (500 MHz, CDCl2F, -110 °C): δ
°C) δ 5.76 (s, 2H, H1,2), 2.27 (t, JH-H ) 7.5 Hz, 4H, H3,4), 1.78
6.79 (s, 3H, mesAr), 2.20 (s, 9H, mesCH ).
(m, 2H, H5); 13C{1H} NMR (100 MHz, CD2Cl2, -87 °C) δ 130.8
(s, C3,4), 32.6 (s, C5,7), 23.0 (s, C6).
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In Situ Generation of [(2-Cl-allyl)Pd(ethylene)2][SbF6] (10-
Cl). A J-Young NMR tube was charged with [(2-Cl-allyl)Pd-
(mes)][SbF6] (5-Cl; 0.010 g, 0.019 mmol) dissolved in ca. 500 µL
of CDCl2F. The yellow solution was frozen at -196 °C, and
approximately 3 equiv (93 Torr, 0.056 mmol) of ethylene was
admitted via a 10.94 mL calibrated gas bulb on a high-vacuum
line. The tube was then moved to a -78 °C dry ice-acetone bath.
The tube was inverted to allow mixing, and the solution turned
from yellow to colorless. Variable-temperature spectra are shown
In Situ Generation of [(Allyl)Pd(2-butyne)2][SbF6] (15-H). A
screw-cap NMR tube was charged with [(allyl)Pd(mes)][SbF6] (5-
H; 0.011 g, 0.020 mmol) dissolved in ca. 400 µL of CDCl2F. The
tube was placed in a -78 °C bath, and 2 equiv of 2-butyne (3.1
µL, 0.040 mmol) was added via syringe. The number of equivalents
of ligand added was NMR via NMR integration. The tube was
shaken to allow for mixing, and a color change from yellow to
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colorless was observed. H NMR (500 MHz, CDCl2F, -120 °C):
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in Figure 4. H NMR (500 MHz CDCl2F, -110 °C): δ 5.38 (m,
δ 6.05 (m, 1H, Hc), 4.72 (d, JH-H ) 6.5 Hz, 2H, Hsyn), 3.72 (d,