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J. Fawcett et al. / Inorganica Chimica Acta 359 (2006) 3535–3539
2.1. (1,2-Bis{di-(4-methoxyphenyl)phosphino}ethane)-
nickel dichloride (II)
solid which was recrystallised from n-hexane/dichloro-
methane to give the product as a pale yellow solid
(0.108 g, 66%). Anal. Calc for C60H64Cl2O8P4Pd requires:
C, 59.34; H, 5.28. Found: C, 60.00; H, 5.60%. m/z (FAB)
1177 [M À Cl]+. 1H NMR (CDCl3): 7.28 (8H, m, 2,6-
s, OCH3), 2.16 (4H, d, JHP = 17.9 Hz, C2H4). 31P{1H}
NMR (CDCl3): 52.8 (s).
A solution of the ligand (0.100 g, 0.19 mmol) in dichlo-
romethane (20 cm3) was added to a stirred solution of
NiCl2 Æ 6H2O (0.048 g, 0.20 mmol) in methanol (40 cm3),
and the mixture stirred for 1 h. Removal of the solvents
in vacuo afforded an orange/brown solid which was recrys-
tallised from n-hexane/dichloromethane to give the prod-
uct as an orange solid (0.112 g, 90%). Anal. Calc. for
C30H32Cl2NiO4P2 requires: C, 55.58; H, 4.94. Found: C,
3
ArH), 6.92 (8H, d, JHH = 8.3 Hz, 3,5-ArH), 3.84 (12H,
2.5. (1,2-Bis{di-(4-methoxyphenyl)phosphino}ethane)-
platinum dichloride (VI)
56.33; H, 5.43%. m/z (FAB) 646 [M]+, 611 [M À Cl]+. H
1
NMR (CDCl3): 7.82 (8H, m, 2,6-ArH), 6.20 (8H, d,
3JHH = 8.5 Hz, 3,5-ArH), 3.87 (12H, s, OCH3), 2.04 (4H,
d, JHP = 17.9 Hz, C2H4). 31P{1H} NMR (CDCl3): 54.5
The ligand (0.125 g, 0.24 mmol) was added to a stirred
solution of [PtCl2(MeCN)2] (0.084 g, 0.20 mmol) in dichlo-
romethane (50 cm3), and the mixture refluxed under nitro-
gen for 2 h. On cooling, the mixture was filtered, the
solvent removed in vacuo to afford an off-white solid which
was washed with n-hexane and methanol to give the prod-
uct as an off-white solid (0.048 g, 26%). Anal. Calc. for
C30H32Cl2O4P2Pt requires: C, 45.92; H, 4.08. Found: C,
46.71; H, 4.16%. m/z (FAB) 748 [M À Cl]+. 1H NMR
(s). IR (Nujol): 314, 293 cmÀ1
.
2.2. Bis-(1,2-bis{di-(4-methoxyphenyl)phosphino}ethane)-
nickel dichloride (III)
An aliquot of the ligand (0.060 g, 0.12 mmol) was added
to a stirred solution of (II) (0.075 g, 0.12 mmol) in dichlo-
romethane (50 cm3), and the mixture stirred under nitrogen
for 2 h. Removal of the solvents in vacuo afforded a dark
brown solid which was recrystallised from n-hexane/dichlo-
romethane to give the product as a light brown solid
(0.108 g, 80%). Anal. Calc. for C60H64Cl2NiO8P4 Æ CH2Cl2
requires: C, 58.53; H, 5.28. Found: C, 59.39; H, 5.04%.
3
3
(CDCl3): 7.72 (8H, dd, JHP = 9.9, JHH = 8.7 Hz, 2,6-
3
ArH), 6.84 (8H, d, JHH = 8.7 Hz, 3,5-ArH), 3.78 (12H,
s, OCH3), 2.18 (4H, d, JHP = 21.7 Hz, C2H4). 31P{1H}
1
NMR (CDCl3): 39.2 (s, JPPt = 3645 Hz).
2.6. Bis-(1,2-bis{di-(4-methoxyphenyl)phosphino}ethane)-
platinum dichloride (VII)
1
m/z (FAB) 1129 [M À Cl]+. H NMR (CDCl3): 7.67 (8H,
3
m, 2,6-ArH), 6.84 (8H, d, JHH = 8.1 Hz, 3,5-ArH), 3.81
An aliquot of the ligand (0.125 g, 0.24 mmol) was added
to a stirred solution of (VI) (0.084 g, 0.24 mmol) in dichlo-
romethane (50 cm3), and the mixture refluxed under nitro-
gen for 2 h, cooled and filtered. Removal of the solvent in
vacuo afforded an off-white solid that was washed with n-
hexane and methanol. The methanol washings were con-
centrated in vacuo, and the product precipitated as a fine
white solid by the addition of n-hexane (0.058 g, 37%).
Anal. Calc. for C60H64Cl2O8P4Pt requires: C, 55.30; H,
4.93. Found: C, 54.06; H, 5.09%. m/z (FAB) 1266
[M À Cl]+. 1H NMR (CDCl3): 7.60 (8H, m, 2,6-ArH),
(12H, s, OCH3), 2.52 (4H, m, C2H4). 31P{1H} NMR
(CDCl3): 47.2 (s).
2.3. (1,2-Bis{di-(4-methoxyphenyl)phosphino}ethane)-
palladium dichloride (IV)
The ligand (0.071 g, 0.14 mmol) was added to a stirred
solution of [PdCl2(MeCN)2] (0.023 g, 0.13 mmol) in dichlo-
romethane (40 cm3), and the mixture gently heated under
nitrogen for 2 h. Upon cooling, the mixture was filtered,
the solvent removed in vacuo to yield the product as a yel-
low solid which was washed with n-hexane (0.015 g, 17%).
Anal. Calc. for C30H32Cl2O4P2Pd requires: C, 51.77; H,
4.60. Found: C, 51.71; H, 5.19%. m/z (FAB) 659
3
6.78 (8H, d, JHH = 8.7 Hz, 3,5-ArH), 3.72 (12H, s,
OCH3), 2.95 (4H, m, C2H4). 31P{1H} NMR (CDCl3):
1
45.6 (s, JPPt = 2364 Hz).
1
3
[M À Cl]+. H NMR (CDCl3): 7.71 (8H, dd, JHP = 11.5,
2.6.1. Crystal structure determinations of [NiCl2(L-L)]
(II) and [PdCl2(L-L)] (IV)
3JHH = 8.7 Hz, 2,6-ArH), 6.86 (8H, dd, JHH = 8.3,
3
4JHP = 1.6 Hz, 3,5-ArH), 3.76 (12H, s, OCH3), 2.26 (4H,
d, JHP = 23.0 Hz, C2H4). 31P{1H} NMR (CDCl3): 61.5
Crystals suitable for single-crystal structural analysis
were grown by slow evaporation from dichloromethane/
hexane solutions. Data were collected on a Bruker Apex
CCDC diffractometer, and full details of data collection
and refinement are given in Table 1.
(s). IR (Nujol): 312, 297 cmÀ1
.
2.4. Bis-(1,2-bis{di-(4-methoxyphenyl)phosphino}ethane)-
palladium dichloride (V)
2.6.2. Structure solution and refinement
An aliquot of the ligand (0.070 g, 0.13 mmol) was added
to a stirred solution of (IV) (0.094 g, 0.13 mmol) in dichlo-
romethane (50 cm3), and the mixture stirred under nitrogen
for 2 h. Removal of the solvents in vacuo afforded a yellow
Structure solution was by Patterson methods. The struc-
ture refinement on F2 employed SHELXTL version 6.10
(SHELXTL, an integrated system for solving, refining and dis-
playing crystal structures) [12]. For all structures hydrogen