Organometallics
Article
addition of H2O (5 mL), removal of volatiles in vacuo, and subsequent
dissolution of the residue in a mixture of methylene chloride (180 mL)
and water (100 mL), acidified with 5 mL of aqueous HCl solution
(37%), for extraction. The aqueous phase was removed and extracted
with methylene chloride (100 mL), and the combined organic phases
were dried over MgSO4 followed by removal of the volatiles in vacuo.
Afterward the obtained residue was washed with tetrahydrofuran (6 ×
20 mL), Et2O (2 × 20 mL), and pentane (2 × 20 mL), which provides
the crude product mixture after drying in vacuo (4.59 g, 9.13 mmol,
70% yield, 81% content of 5 determined by 31P NMR spectroscopy in
CDCl3). Crystallization of this crude product mixture from hot CHCl3
gave colorless needles of the pure ligand 7 (682 mg, 28%).
1H, H5), 7.13−7.07 (s, 1H, H26), 7.07−7.01 (m, 1H, H6), 6.85 (d,
3J(H−H) = 7.6 Hz, 1H, H20), 6.70 (d, 3J(H−H) = 7.6 Hz, 1H. H10),
3.71 (s, br, 3H, OMe1), 3.05 (s, 3H, OMe2), 0.49 (s, 3H, PdMe).
13C{1H} NMR (75 MHz, CDCl3): δ 156.1 (s, C19), 155.8 (s, C9),
150.9 (s, py1), 137.7 (s, py3, C16), 136.2 (d, J = 7.5 Hz), 135.5 (d, J =
5.2 Hz, C26), 135.4 (d, J = 7.6 Hz), 133.4 (d, 2J(C−P) = 1.6 Hz, C6),
132.0 (s), 131.8 (s, C24), 131.3 (s, C14), 130.3 (s, C4), 129.9 (s, br,
C3, 5), 127.1 (s), 126.9 (s, C11), 126.4 (s, C21), 126.0 (d, 3J(C−P) =
3
8.5 Hz, C25), 125.5 (d, J(C−P) = 10.5 Hz, C15), 125.1−124.7 (m,
py2, C16), 122.0 (s, C22), 120.9 (s, C12), 107.1 (s, C20), 105.3 (s,
C10), 56.5 (s, br, OMe2), 53.7 (s, OMe1), −0.17 (s, Pd-Me). 31P{1H}
NMR (121 MHz, CDCl3): δ +47.0. Due to overlapping peaks, most
quaternary carbon atoms could not be assigned and detected. Anal.
Calcd for C35H31NPPdSO5: C 58.79, H 4.37, N 1.96, S 4.48. Found: C
57.15, H 4.32, N 2.11, S 4.42. As observed from X-ray diffraction the
compound cocrystallizes with CHCl3 and the residual solvent could
not be removed.
1H NMR (500 MHz, CDCl3): δ 10.62 (d, 1J(H−P) = 674.3 Hz, 1H,
3
4
H-P), 8.50 (dd, J(H−H) = 7.7 Hz, J(H−P) = 4.8 Hz, 1H, H3),
8.12−8.05 (m, 2H, H14, 24), 7.73 (m, 1H, H4), 7.60−7.56 (m, 3H,
H11, 12, 22), 7.47 (m, 2H, H21, 25), 7.36−7.28 (m, 2H, H5, 15), 7.26
3
3
(d, J(H−H) = 7.3 Hz, 1H, H26), 7.12 (dd, J(H−P) = 18.0 Hz,
3J(H−H) = 7.3 Hz, 1H, H16), 7.00 (dd, J(H−H) = 6.7, 2.0 Hz, 1H,
Synthesis of [κ1-(N)-tmeda][{κ2-(P,O)-2-(bis-8-methoxynaph-
thalene-1-phosphine)benzene sulfonate}PdMe]2, 10. This in-
termediary product for the reaction of 7 to 9 could be obtained as a
pale yellow solid from a synthesis of 9 without addition of pyridine.
Precipitation of 10 by addition of Et2O (yield 67.2%) was followed by
recrystallization from CHCl3/pentane. The low solubility of 10 in
CHCl3 precludes characterization by 13C NMR spectroscopy. 1H
NMR (300 MHz, CDCl3): δ 8.24 (dd, J = 7.4, 3.7 Hz, 1H), 7.90 (d,
J = 8.1 Hz, 1H), 7.79 (d, J = 8.2 Hz, 1H), 7.65 (dd, J = 14.0, 7.3 Hz,
1H), 7.53−7.36 (m, 5H), 7.34−7.19 (m, 4H), 7.09 (t, J = 7.5 Hz, 1H),
7.03−6.86 (m, 3H), 6.66 (d, J = 6.6 Hz, 1H), 3.68 (s, 3H), 2.98 (s,
3H), 2.17 (s, 3H), 1.55 (s, 3H), 0.16 (s, 3H). 31P{1H} NMR (121
MHz, CDCl3): δ +47.6. Anal. Calcd for C64H66N2P2Pd2S2O10: C
56.43, H 4.88, N 2.06, S 4.71. Found: C 53.18, H 4.77, N 2.01, S 4.17.
As observed from X-ray diffraction the compound cocrystallizes with
CHCl3 and the residual solvent could not be removed.
3
3
H10), 6.93 (dd, J(H−P) = 14.4 Hz, J(H−H) = 7.7 Hz, 1H, H6),
3
6.80 (d, J(H−H) = 7.7 Hz, 1H, H20), 3.89 (s, 3H, OMe1), 3.22 (s,
3H, OMe2). 13C{1H} NMR (75 MHz, CDCl3): δ 154.9 (s, C9), 154.2
2
2
(s, C19), 151.3 (d, J(C−P) = 8.2 Hz, C2), 136.8 (d, J(C−P) =
9.2 Hz, C26), 135.7 (d, 2J(C−P) = 9.1 Hz, C16), 135.5 (s, C23), 135.4
(s, C13), 134.5 (d, 4J(C−P) = 3.2 Hz, C24), 134.3 (s, C14), 133.9 (d,
4J(C−P) = 3.3 Hz, C4), 133.9 (d, J(C−P) = 4.1 Hz, C6), 130.4
2
3
3
(d, J(C−P) = 8.7 Hz, C3), 129.8 (d, J(C−P) = 12.2 Hz, C5), 128.3
(s, C11), 127.7 (s, C21), 126.3 (d, 3J(C−P) = 15.0 Hz, C25), 125.8 (d,
3J(C−P) = 14.7 Hz, C15), 125.4 (d, 2J(C−P) = 5.1 Hz, C8), 124.6 (d,
2J(C−P) = 5.3 Hz, C18), 122.5 (s, C12), 121.8 (s, C22), 118.1
1
1
(d, J(C−P) = 94.7 Hz, C17), 117.0 (d, J(C−P) = 89.7 Hz, C7),
1
115.9 (d, J(C−P) = 92.8 Hz, C1), 107.9 (s, C10), 107.8 (s, C20),
56.3 (s, OMe1), 55.1 (s, OMe2). 31P NMR (121 MHz, CDCl3):
1
δ +16.5 (ddd, J(H−P) = 674.3, J(H−P) 32.2, 15.5 Hz). HR-ESI-MS
(neg., MeCN): m/z = 501.0936 (M−). Calcd for C28H22PSO5: m/z =
501.0926 (M − H+).
Single-Crystal X-ray Structure Determinations. 9: yellow
prism, C34H30NO5PPdS, Mr = 702.03; monoclinic, space group C2/c
(No. 15), a = 18.3019(3) Å, b = 15.5260(3) Å, c = 24.6690(5) Å, β =
93.5722(9)°, V = 6996.2(2) Å3, Z = 8, λ(Mo Kα) = 0.71073 Å, μ =
0.674 mm−1, ρcalcd = 1.333 g cm−3, T = 173(1) K, F(000) = 2864, θmax
25.47°, R1 = 0.0225 (5970 observed data), wR2 = 0.0579 (all 6482
data), GOF = 1.060, 391 parameters, Δρmax/min = 0.32/−0.34 e·Å−3.
Unresolved solvent molecules had to be removed with the SQUEEZE
procedure. 10: yellow fragment, C64H66N2O10P2Pd2S2·CHCl3, Mr =
1481.44; monoclinic, space group P21/c (No. 14), a = 23.1506(9) Å,
b = 14.7312(6) Å, c = 24.5348(9) Å, β = 110.6878(17)°, V = 7827.7(5)
Å3, Z = 4, λ(Mo Kα) = 0.71073 Å, μ = 0.705 mm−1, ρcalcd = 1.257
g·cm−3, T = 123(1) K, F(000) = 3024, θmax 25.46°, R1 = 0.0344 (13 066
observed data), wR2 = 0.0935 (all 14451 data), GOF = 1.056,
785 parameters, Δρmax/min = 1.65/−1.01 e·Å−3. Besides the solvent
molecule, well located in the difference Fourier maps, unresolved
solvent molecules remained and had to be removed with the SQUEEZE
procedure. Crystallographic data (excluding structure factors) for the
structures reported in this paper have been deposited with the
Cambridge Crystallographic Data Centre as supplementary publication
nos. CCDC-853890 (9) and CCDC-853891 (10). Copies of the data
can be obtained free of charge on application to CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK (fax: (+44)1223-336-033; e-mail:
Supporting Information.
Synthesis of [{κ2-(P,O)-2-(Bis-2-methylthiophenylphosphine)-
benzenesulfonate}PdMe (pyridine)], 8. The phosphine sulfonate
5 (348 mg, 0.80 mmol, 1 equiv) was dissolved in methylene chloride
(10 mL), and (tmeda)PdMe2 (202 mg, 0.80 mmol, 1 equiv) was
added. Evolution of gas was observed during formation of a yellow
solution, which was stirred for 30 min. Pyridine was added (0.5 mL,
excess), and the solution became orange. After stirring for 1 h at room
temperature the solution was reduced to 5 mL, and the complex
precipitated by addition of Et2O (20 mL). The liquid was removed by
filtration, and the obtained solid was reprecipitated from methylene
chloride (10 mL)/Et2O (20 mL). After filtration and removal of
volatiles 8 was obtained as an off-white solid (145 mg, 0.23 mmol,
29%). Crystallization of this compound could not be achieved, and
residual solvent has been observed by 1H NMR spectroscopy; hence, a
low EA was obtained.
1H NMR (500 MHz, CDCl3): δ 8.88 (s, 1H), 8.40 (s, 1H), 7.85 (s,
1H), 7.67−7.08 (m, 10H), 2.42 (s, 4H), 0.69 (s, 2H). 31P NMR (121
MHz, CD2Cl2): δ +34.5. Anal. Calcd for C26H26PNS3O3Pd: C 49.25,
H 4.13, N 2.21, S 15.17. Found: C 47.26, H 4.03, N 1.86, S 14.76.
Synthesis of [{κ2-(P,O)-2-(bis-8-methoxynaphthalene-1-
phosphine)benzenesulfonate}PdMe (pyridine)], 9. 7 (200 mg,
0.40 mmol, 1 equiv) was dissolved in methylene chloride (10 mL), and
(tmeda)PdMe2 (100 mg, 0.40 mmol, 1 equiv) was added. Evolution of
gas was observed during formation of a pale yellow solution, which was
stirred for 20 min followed by pyridine addition (0.25 mL, excess).
After stirring for 1 h at room temperature the solution was reduced to
2 mL and precipitated by addition of pentane (8 mL). The solvent was
filtered off, and the obtained solid was recrystallized from CHCl3
(7 mL)/pentane (20 mL). A 150 mg amount of complex 9 (0.21
mmol, 53%) was obtained as yellow crystals.
ASSOCIATED CONTENT
■
S
* Supporting Information
Additional NMR spectroscopic data including detailed peak
assignments and tables for interpretation of NOESY spectra.
Representative examples for polymer characterization and
crystallographic data for complexes 9 and 10. This material is
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1H NMR (500 MHz, CDCl3): δ 8.75 (d, J(H−H) = 5.3 Hz, 2H,
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Hpy1), 8.39−8.28 (m, 1H, H3), 7.94 (d, J(H−H) = 8.1 Hz, 1H,
3
3
H14), 7.86 (d, J(H−H) = 8.1 Hz, 1H, H24), 7.67 (t, J(H−H) = 7.6
Hz, 1H, Hpy3), 7.55−7.39 (m, 5H, H4, 11, 12, 21, 22), 7.39−7.32 (m,
1H, H15), 7.32−7.23 (m, 4H, Hpy2, 16, 25), 7.16 (t, 3J(H−H) = 7.6 Hz,
6610
dx.doi.org/10.1021/om200734x | Organometallics 2011, 30, 6602−6611