44.9 (s, N(C4H8)NCH3), 46.5 (s, N(CH2CH2)2NCH3), 54.1 (s,
N(CH2CH2)2NCH3), 55.8 (d, 2JCP = 16.0 Hz, Ph2PCH2CH), 127.2
(d, 3JCP = 7.0 Hz, m-PhC), 127.3 (d, 3JCP = 7.0 Hz, m-PhC), 127.4
NMR(d6-DMSO): the spectrum was so broad that assignment was
1
impossible; limited solubility precluded acquisition of 13C{ H}
1
NMR spectral data; 31P{ H} NMR (121.4 MHz, d6-DMSO) d
2
(s, p-PhC), 127.5 (s, p-PhC), 131.8 (d, JCP = 15.0 Hz, o-PhC),
ppm: +50.4 (m1 = 24 Hz); MS (ES+) m/z: 441.9 (M–Cl+).
2
2
1
131.8 (d, JCP = 15.0 Hz, o-PhC), 138.1 (d, JCP = 14.0 Hz, i-
Synthesis of [PdCl2(3)], 8. An analogous procedure to that
used for the preparation of 6 was adopted, involving reaction of
PdCl2(MeCN)2 (0.16 g, 6.34 × 10−4 mol) with 3 (0.20 g, 6.34 ×
10−4 mol) in CH2Cl2 (20 cm3). This lead to the isolation of 8 as
a yellow powder (0.25 g, 80%) (calc.: C18H22NSPPdCl2 C, 43.87;
PhC), 138.4 (d, JCP = 14.0 Hz, i-PhC); 31P{ H} (121.4 MHz,
CDCl3) d ppm: −18.6 (s); MS (ES+) m/z: 327.2 (MH+).
1
1
Bubbling gaseous HCl through an ethereal solution of 4
(0.85 g, 2.60 × 10−3 mol) resulted in the immediate precipitation
of the mono-hydrochloride salt 5 as a white solid, which was
isolated in near-quantitative yield (0.93 g, 98%). Crystals of X-
ray quality were grown from CHCl3/Et2O. (Calc.: C20H28N2PCl
C, 66.19; H, 7.79; N, 7.72. Found: C, 66.36; H, 7.76; N,
1
H, 4.51; N, 2.84. Found: C, 43.93; H, 4.62; N, 2.82). H NMR
(299.9 MHz, d6-DMSO) d ppm: 2.80–3.45 (m, 8H, CH2), 3.82
(m, 2H, CH2), 4.34 (m, 2H, CH2), 7.51 (m, 6H, m-/p-PhH), 7.89
(m, 4H, o-PhH); the low solubility of 8 precluded the acquisition
of 13C NMR spectra; 31P NMR (121.4 MHz, d6-DMSO) d ppm:
1
4
7.92). H NMR (499.7 MHz, CDCl3) d ppm: 1.05 (d, JPH
=
6.4 Hz, 3H, CH2CH(CH3)NCH3), 1.90 (m, 1H, N(C4H8)N),
2.10–2.35 (m, 2H, N(C4H8)N), 2.45–2.85 (m, 6H, N(C4H8)N,
Ph2PCH2CH), 2.95–3.34 (m, 5H, N(C4H8)N, CH3N(C4H8)N, and
Ph2PCH2CH), 7.18–7.32 (m, 8H, o-/m-PhH), 7.41 (s, p-PhH),
+49.8 (m1 = 27 Hz); MS (ES+) m/z: 457.9 (M–Cl+).
2
Synthesis of [PdCl(Cy2PC2H4NMe3)(1-j2-PN)]Cl2, 9. A solu-
tion (D2O) of 6 (0.018 g, 3.68 × 10−5 mol) was treated under
12.27 (br s, m1 = 37.5 Hz, 1H, NH+); H (499.7 MHz, CDCl3,
N2 with Cy2PC2H4NMe3Cl (0.012 g, 3.68 × 10−5 mol). 31P{ H}
1
1
2
223 K) d ppm: 1.08 (s, 3H, CH2CH(CH3)N), 1.86–2.09 (m, 2H,
NMR (81.0 MHz, D2O) d ppm: +54.8 (d, 2JPP = 12.0 Hz), +44.1
Ph2PCH2CH and N(C4H8)N), 2.32–2.88 (m, 8H, Ph2PCH2CH,
N(C4H8)N, N(C4H8)NCH3, and Ph2PCH2CH), 3.07 (m, 3H,
N(C4H8)N), 3.34 (m, 1H, N(C4H8)N), 7.26–7.41 (m, 8H, o-/m-
(d, 2JPP = 12.0 Hz).
Synthesis of [PdCl2(1-j3-PNN)]2[Mg(SO4)2(H2O)4], 10. Un-
der air, complex 6 (0.10 g, 2.08 × 10−4 mol) was treated with
MgSO4 (1.01 g, 8.352 × 10−3 mol) in methanol (10 cm3) and the
resulting mixture allowed to stir at room temperature for 36 h. The
excess unreacted MgSO4 and MgCl2 by-product were removed by
filtration and the solvent removed in vacuo to afford 10 as a vivid
yellow powder (yield 0.22 g, 89%). Crystals of X-ray quality were
grown by slow evaporation of a dilute methanolic solution of the
product under air (CHN analyses proved unreliable as a result of
desolvation and decomposition). For spectroscopic assignments
see Fig. 2. 1H NMR (299.9 MHz, CD3OD) d ppm: 2.67 (d,
4JPH = 5.0 Hz, 3H, CH3N), 2.95 (m, 4H, MeNCH2CH2), 3.08
(m, 4H, MeNCH2CH2), 3.83 (m, 2H, Ph2PCH2CH2), 3.96 (m, 2H,
Ph2PCH2CH2N), 7.58 (m, 4H, m-PhH), 7.60 (m, 6H, p-PhH), 7.96
(m, 4H, o-PhH) {NB. the resonance due to the solvent obscures
PhH), 7.50 (s, p-PhH), 11.72 (br s, m1 = 33.3 Hz, 1H, NH+);
2
1
3
13C{ H} (100.6 MHz, CDCl3) d ppm: 14.4 (d, JPC = 8.0 Hz,
CH2CH(CH3)N), 31.9 (s, Ph2PCH2CH), 42.7 (s, N(C4H8)NCH3),
46.3 (s, N(CH2CH2)2NCH3), 52.0 (s, N(CH2CH2)2NCH3), 56.9 (s,
Ph2PCH2CH), 127.4 (d, 3JPC = 7.5 Hz, m-PhC), 127.6 (d, 3JPC
=
7.5 Hz, m-PhC), 127.7 (s, p-PhC), 127.9 (s, p-PhC), 131.5 (d, 2JPC
=
2
19.5 Hz, o-PhC), 132.1 (d, JPC = 19.5 Hz, o-PhC), 137.5 (br s,
i-PhC); 31P{ H} (121.4 MHz, CDCl3) d ppm: −17.3 (s); MS (ES+,
1
MeOH) m/z: 343.4 [M–Cl + Me]+.
Synthesis of [PdCl2(1)], 6. To a Schlenk flask charged with
PdCl2(MeCN)2 (0.11 g, 4.24 × 10−4 mol) was added 1 (0.13 g,
4.26 × 10−4 mol) and CH2Cl2 (20 cm3). The mixture was stirred at
room temperature for 12 h, which resulted in the formation of a
fine yellow solid. The precipitate was isolated by cannula filtration,
washed repeatedly with hexane and diethyl ether and dried in vacuo
to afford 6 as a bright yellow powder (yield 0.14 g, 68%). (calc.:
C19H25N2PPdCl2 C, 46.59; H, 5.16; N, 5.72. Found: C, 46.17; H,
5.15; N, 5.82). For spectroscopic assignments see Fig. 2. 1H NMR
(400.1 MHz, D2O) d ppm: 2.78 (d, 4JPH = 5.1 Hz, 3H, Hg), 3.05 (m,
2H, Hf), 3.12 (m, 2H, Ha), 3.19 (m, 2H, Hd), 3.37 (m, 2H, Hb), 3.95
(m, 2H, He), 4.07 (m, 2H, Hc), 7.58 (m, 4H, m-PhH), 7.64 (m, 2H,
1
a 2H multiplet}; 13C{ H} (100.6 MHz, CD3OD) d ppm: 34.4 (d,
2
1JPC = 12.0 Hz, Ph2PCH2), 44.9 (d, JPC = 2.5 Hz, CH3N), 56.5
2
(s, MeN(C2H4)2), 57.0 (s, MeN(C2H4)2), 57.5 (d, JPC = 4.0 Hz,
Ph2PCH2CH2), 126.5 (d, 1JPC = 53.0 Hz, i-PhC), 129.4 (d, 3JPC
=
=
12.0 Hz, m-PhC), 132.6 (d, 4JPC = 2.5 Hz, p-PhC), 133.2 (d, 2JPC
1
11.5Hz, o-PhC); 31P{ H} (121.4 MHz, CD3OD) d ppm: +46.5;MS
(ES+, MeOH) m/z: 455.0 (M–Cl+); MS (ES−, MeOH) m/z: 97.0
([HSO4]−); KM (MeOH, 5 × 10−3 mol, 22.5 ◦C: 360 X cm2 mol−1).
1
p-PhH), 7.96 (m, 4H, o-(PhH); 13C{ H} 100.6 MHz, D2O) d ppm:
Synthesis of [PdCl(Me)(2-j2-PN)], 11. To a Schlenk flask
charged with PdClMe(COD) (8.40 × 10−2 g, 3.20 × 10−4 mol)
was added 1 (0.100 g, 3.20 × 10−4 mol) in CH2Cl2 (10 cm3).
The resulting mixture was allowed to stir at room temperature
for 18 h with all light excluded from the Schlenk flask. The
solvent was then removed under vacuum, the product extracted
with hexane and dried thoroughly in vacuo to afford a yellow
powder (yield 0.11 g, 76%). 1H NMR (499.8 MHz, CDCl3, 223 K)
d ppm: 0.51 (s, 3H, PdCH3), 2.21 (s, 3H, CH3N(C4H8)N), 2.38–
2.66 (m, 6H, MeN(C4H8)N, Ph2PCH2CH2 and MeN(C4H8)N),
2.73–2.93 (m, 4H, MeN(C4H8)N and Ph2PCH2CH2N), 4.12 (m,
2H, MeN(C4H8)N), 7.41–7.56 (m, 6H, m-PhH and p-PhH), 7.64
35.0 (d, 1JPC = 32.0 Hz, Ph2PCH2), 45.9 (s, CH3N), 57.0 (s, CH2),
1
57.6 (s, CH2), 58.0 (s, Ph2PCH2CH2), 126.0 (d, JPC = 52.5 Hz,
i-PhC), 130.3 (d, 3JPC = 11.5 Hz, m-PhC), 133.8 (d, 4JPC = 7.0 Hz,
2
1
p-PhC), 134.0 (d, JPC = 12.0 Hz, o-PhC); 31P{ H} (121.4 MHz,
D2O) d ppm: +45.7 (s); 31P{ H} (121.4 MHz, CD3OD) d ppm:
1
+46.5 (s); MS (MALDI ToF, Dithranol matrix) m/z: 455.0 (M–
Cl+); KM (MeOH, 5 × 10−3 mol, 22.5 ◦C: 68 X cm2 mol−1).
Synthesis of [PdCl2(2)], 7. An analogous procedure to that
used for the preparation of 6 was adopted, involving reaction of
PdCl2(MeCN)2 (0.17 g, 6.68 × 10−4 mol) with 2 (0.20 g, 6.68 ×
10−4 mol) in CH2Cl2 (20 cm3). This lead to the isolation of 7 as
a dull yellow powder (yield 0.21 g, 67%) (calc.: C18H22NOPPdCl2
C, 45.35; H, 4.66; N, 2.94. Found: C, 45.18; H, 4.57; N, 2.78). 1H
1
(m, 4H, o-PhH); 13C{ H} (125.7 MHz, CDCl3) d ppm: 30.8
1
(d, JPC = 27.5 Hz, Ph2PCH2CH2), 46.5 (s, CH3N(CH2CH2)2),
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The Royal Society of Chemistry 2006
Dalton Trans., 2006, 4134–4145 | 4143
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