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M.M. Ebrahim et al. / Polyhedron 26 (2007) 1277–1284
3
Hg(II) halide complexes of a BPMO ligand 1,2-bis(diph-
enylphosphino)ethane monoxide (dppeO).
7.89 (m, 20H). 31P NMR : 29.46 (d, JP–P = 57.5), 33.38
(d, JP–P = 57.5, JHg–P = 6422).
3
1
2. Experimental
2.2.4. [HgI2(dppeO)]n (3)
Complex 3 was obtained in the same way as 1 using mer-
cury(II) iodide (0.22 g, 0.48 mmol) and dppeO (0.2 g,
0.48 mmol). The product obtained was recrystallized by
slow evaporation of a chloroform solution. Yield: 0.35 g,
83%; m.p.: 212–214 °C. Anal. Calc. for C26H24Hg I2OP2:
C, 35.94; H, 2.78. Found. C, 35.87; H, 2.75%. IR (cmÀ1):
3053, 2906, 1588, 1484, 1436, 1411, 1156, 1120, 1098,
998, 739, 726, 691, 538, 507, 494, 474. 1H NMR: 2.75
(br, 2H), 2.92 (br, 2H), 7.45–7.86 (m, 20H). 31P NMR:
All reactions were carried out under an atmosphere of
dry nitrogen. Reactants and reagents were obtained from
Aldrich Chemical Company and used without further puri-
fication. The solvents were dried and distilled using stan-
dard methods [13].
2.1. Instrumentation
1
1
3
The H and 31P–{1H}NMR spectra were recorded in
6.34 (br, JHg–P = 4366), 32.93 (d, JP–P = 54.9).
CDCl3 solution on a Bruker DPX400 spectrometer at
400.13 and 161.98 MHz, referenced relative to residual
CHCl3 and external 85% H3PO4, respectively. The IR spec-
tra in the interval of 4000–400 cmÀ1 were recorded on a
Perkin–Elmer 1720X FT-IR spectrometer using KBr pel-
lets. Elemental analyses were performed at the Ecole
2.2.5. [HgCl2(dppeO)2] (4)
A solution of mercury(II) chloride (0.098 g, 0.36 mmol)
in methanol was added dropwise to a solution of dppeO
(0.3 g, 0.72 mmol) in dichloromethane. The mixture was
stirred for 3 h. White feathery crystals obtained after slow
evaporation of the solvent were washed with cold methanol
and dried in vacuo. Yield: 0.29 g, 75%; m.p.: 250 °C. Anal.
Calc. for C52H48Cl2HgO2P4: C, 56.76; H, 4.40. Found. C,
56.47; H, 4.35%. IR (cmÀ1): 3051, 2912, 1573, 1484,
1436, 1188, 1121, 1104, 997, 738, 728, 693, 540, 517, 506,
479. 1H NMR: 2.90 (br, 8H), 7.27–7.91 (m, 40H). 31P
´
d’ingenieurs de Fribourg, Switzerland.
2.2. Synthesis of compounds
2.2.1. 1,2-Bis(diphenylphosphino)ethane monoxide (dppeO)
The phosphonium salt obtained by the reaction of 1,2-
bis(diphenylphosphino)ethane (dppe) with benzyl bromide
in dry toluene, was hydrolysed with aqueous sodium
hydroxide to yield the ligand, as reported previously [14].
IR (cmÀ1): 3052, 1937, 2903, 1588, 1480, 1435, 1182,
1122, 1106, 1069, 1025, 997, 881, 783, 727, 692, 712, 536,
513, 504, 474. 1H NMR : 2.28 (br, 4H), 7.29–7.71 (m,
1
NMR: 28.75 (br, JHg–P = 4654), 34.08 (br).
2.2.6. [HgBr2(dppeO)2] (5)
Complex 5 was prepared in the same way as for 4 using
mercury(II) bromide (0.13 g, 0.36 mmol). Yield: 0.29 g,
70%. m.p.: 216–218 °C. Anal. Calc. for C52H48Br2HgO2P4:
C, 52.52; H, 4.07. Found. C, 51.92; H, 4.06%. IR (cmÀ1):
3429, 3051, 2910, 1573, 1484, 1436, 1190, 1121, 1103,
996, 737, 727, 693, 539, 516, 507, 478. 1H NMR: 2.88
3
20H). 31P NMR : À11.68 (d, JP–P = 48.4), 33.18 (d,
3JP–P = 48.4).
2.2.2. [HgCl2(dppeO)]n (1)
(br, 8H), 7.45–7.93 (m, 40H). 31P NMR: 21.19 (br, 1JHg–P
=
To a methanolic solution of mercury(II) chloride
(0.13 g, 0.48 mmol), solid dppeO (0.2 g, 0.48 mmol) was
added in portions and allowed to stir overnight. The white
precipitate obtained was filtered, washed with cold metha-
nol and recrystallized from acetonitrile. Yield: 0.27 g, 83%;
m.p.: 253–255 °C. Anal. Calc. for C26H24Cl2HgOP2: C,
45.53; H, 3.53. Found. C, 45.93; H, 3.51%. IR (cmÀ1):
3054, 2913, 1589, 1436, 1160, 1121, 1103, 997, 741, 725,
3874), 33.21 (br).
2.2.7. [HgI2(dppeO)2] (6) Æ CHCl3
Complex 6 was prepared in the same way as for 4 using
mercury(II) iodide (0.16 g, 0.36 mmol). The product was
crystallized in chloroform. Yield: 0.35 g, 75%; m.p.: 196–
198 °C. Anal. Calc. for C53H49Cl3HgI2O2P4: C, 45.38; H,
3.52. Found. C, 45.82; H, 3.53%. IR (cmÀ1): 3052, 2942,
1589, 1483, 1436, 1184, 1120, 1103, 997, 736, 692, 538,
508, 478. 1H NMR: 2.70–2.83 (m, 8H), 7.27–7.88 (m,
1
690, 540, 516, 506, 476. H NMR : 2.87–2.97 (m, 2H),
3.08–3.13 (m, 2H), 7.40–7.91 (m, 20H). 31P NMR : 33.40
3
3
1
1
(d, JP–P = 58.9), 37.12 (d, JP–P = 58.9, JHg–P = 7449).
40H). 31P NMR: 4.32 (br, JHg–P = 3042), 33.14 (br).
2.2.3. [HgBr2(dppeO)]n (2)
2.3. X-ray crystallography
The reaction was carried out as for 1 using mercury(II)
bromide (0.17 g, 0.48 mmol). The product obtained was
recrystallized by slow evaporation of a chloroform solu-
tion. Yield: 0.32 g, 87%; m.p.: 225–227 °C. Anal. Calc. for
C26H24Br2HgOP2: C, 40.30; H, 3.12. Found. C, 40.21; H,
3.08%. IR (cmÀ1): 3054, 2907, 1589, 1483, 1435, 1409,
1164, 1121, 1101, 1069, 1026, 997, 739, 726, 690, 540,
Single crystals of 2 and 3 were obtained by slow evapo-
ration of a chloroform solution. Well formed crystals of 4
were obtained as a DMSO solvate by mixing two equiva-
lents of dppeO, 1 equiv. of HgCl2 and one equivalent of
dimethyltin dichloride, in DMSO and allowed to stand.
Crystals of 5 were grown from a dichloromethane solution
by vapour diffusion of hexane. The intensity data were
1
515, 476. H NMR : 2.89 (br, 2H), 3.06 (br, 2H), 7.42–