Table 5 Crystal and structure refinement data for cis-[PtI(Me){C6H4(PPh2)-2}2]ؒC6H6 15 and [Rh{C6H4(PPh2)-2}3]ؒCH2Cl2 25
15
25
Chemical formula
M
C37H31IP2PtؒC6H6
937.70
C54H42P3RhؒCH2Cl2
971.69
Crystal system
Space group
Monoclinic
Pn
Monoclinic
P21/c
a/Å
b/Å
c/Å
13.494(1)
9.409(2)
14.991(2)
95.27(1)
1895.3(9)
2
23.145(22)
9.425(3)
21.756(10)
104.75(2)
4589(5)
β/Њ
U/Å3
Z
4
T/K
298(1)
144.8
3148
3056 [I > 3σ(I)]
0.030
293(1)
54.6
7601
5327 [I > 3σ(I)]
0.085
µ(Cu-Kα)/cmϪ1
Unique reflections
Used reflections
R (used reflections)
Rw (used reflections)
0.038
0.096
8 J. G. Hartley, L. M. Venanzi and D. C. Goodall, J. Chem. Soc., 1963,
3930.
9 S. Harder, L. Brandsma, J. A. Kanters, A. Duisenberg and J. van
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10 M. A. Bennett, S. K. Bhargava, D. C. R. Hockless, L. L. Welling and
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11 G. Longoni, P. Chini, F. Canziani and P. Fantucci, Gazz. Chim. Ital.,
1974. 104, 249.
evaporation to dryness the benzene eluate gave complex 25 as
a colourless oily solid, which was purified by recrystallisation
from CH2Cl2–ethanol. The yield was 0.25 g (23%). Crystals
suitable for X-ray structural analysis were obtained from
CH2Cl2–hexane at Ϫ5 ЊC. IR (KBr): 1552m and 724s cmϪ1
.
EI-MS: m/z 810, [M Ϫ Ph]ϩ; 701, [M Ϫ PPh2]ϩ; and 625, [M Ϫ
C6H4PPh2]ϩ.
12 H. P. Abicht and K. Issleib, J. Organomet. Chem., 1978, 149, 209;
H. P. Abicht and K. Issleib, J. Organomet. Chem., 1980, 185, 265.
13 M. A. Bennett, D. E. Berry, S. K. Bhargava, E. J. Ditzel, G. B.
Robertson and A. C. Willis, J. Chem. Soc., Chem. Commun., 1987,
1613.
14 M. A. Bennett and D. L. Milner, J. Am. Chem. Soc., 1969, 91, 6983.
15 J. S. Valentine, J. Chem. Soc., Chem. Commun., 1973, 857.
16 D. J. Cole-Hamilton and G. Wilkinson, J. Chem. Soc., Dalton
Trans., 1977, 797.
17 P. E. Garrou, Chem. Rev., 1981, 81, 229.
18 C. Eaborn, K. J. Odell and A. Pidcock, J. Chem. Soc., Dalton Trans.,
1978, 357.
19 C. Eaborn, A. Kundu and A. Pidcock, J. Chem. Soc., Dalton Trans.,
1981, 933.
[IrCl{C6H4(PPh2)-2}2(PPh3)] 28. A stirred suspension of
2-LiC6H4PPh2, prepared as above from 2-BrC6H4PPh2 (1.0 g,
2.9 mmol) in ether (30 cm3) and BunLi (2.2 cm3 of 1.6 M
solution in hexane), was treated with [IrCl3(SEt2)3] (450 mg,
0.79 mmol) in small portions at room temperature and the
mixture stirred overnight. The ether was stripped and the solid
residue extracted with benzene (3 × 50 cm3). The extract was
concentrated under reduced pressure to ca. 30 cm3 volume and
the crude product 28 precipitated as a yellow solid, which was
purified by chromatography [CH2Cl2, alumina (grade 1)] and
recrystallisation from CH2Cl2–hexane. The yield was 0.28 g
(35%). FAB-MS: m/z 1012, [M]ϩ; 977, [M Ϫ Cl]ϩ; 750, [M Ϫ
PPh3]ϩ; and 715, [M Ϫ Cl Ϫ PPh3]ϩ.
20 G. K. Anderson and R. J. Cross, J. Chem. Soc., Dalton Trans., 1979,
1246; G. K. Anderson and R. J. Cross, J. Chem. Soc., Dalton Trans.,
1980, 712.
21 P. S. Pregosin and R. W. Kunz, 31P and 13C NMR of Transition Metal
Phosphine Complexes, Springer, Berlin, 1979.
X-Ray crystallography of cis-[PtI(Me){C6H4(PPh2)-2}2]ؒC6H6
15 and [Rh{C6H4(PPh2)-2}3]ؒCH2Cl2 25
22 J. D. Ruddick and B. L. Shaw, J. Chem. Soc. A, 1969, 2801.
23 T. G. Appleton, H. C. Clark and L. E. Manzer, J. Organomet.
Chem., 1974, 65, 275.
Selected crystal data and details of data collection and pro-
cessing are in Table 5. Crystals of complex 25 were generally of
poor quality and readily lost solvent, which probably accounts
for the 24–50% decrease in intensity during data collection of
three check reflections measured at 90 min intervals. For 15
there was a 5% decrease in intensity under the same conditions.
Its absolute structure was clearly established with a Flack53
parameter of 0.018(8). Data reduction and refinement com-
putations were performed with XTAL 3.0.54
24 G. García and G. Lopez, Inorg. Chim. Acta, 1981, 52, 87.
25 M. B. Smith and A. M. Z. Slawin, Inorg. Chim. Acta, 2000, 299,
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26 D. D. Ellis, G. Harrison, A. G. Orpen, H. Phetmung, P. G. Pringle,
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27 B. L. Shaw and A. C. Smithies, J. Chem. Soc. A, 1967, 1047.
28 L. Dahlenburg, J. Organomet. Chem., 1983, 251, 347.
29 G. del Piero, G. Perego, A. Zazzetta and M. Cesari, Crystal Struct.
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30 K. von Deuten and L. Dahlenburg, Crystal Struct. Commun., 1980,
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CCDC reference number 186/2169.
31 R. J. McKinney, C. B. Knobler, B. T. Huie and H. D. Kaesz,
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32 N. C. Rice and J. D. Oliver, J. Organomet. Chem., 1978, 145, 121.
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34 N. W. Alcock, K. H. Bryars and P. G. Pringle, J. Chem. Soc., Dalton
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