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A.J. Canty et al. / Journal of Organometallic Chemistry 689 (2004) 672–677
Pt(Tol)2(bpy) (0.0398 g, 0.080 mmol) in acetone (5 ml).
The solution was stirred at ambient temperature for
12 h, the solvent removed in a vacuum, and the solid
washed with diethyl ether (3 ꢅ 1 ml). The solid was
recrystallised from CH2Cl2/diethyl ether to give orange
3.7. X-ray data collection and structure determination,
and refinement for complexes 5 and 10
Crystals of 5 and 10 ꢂ CHCl3 were obtained by
recrystallisation from CHCl3/diethyl ether and CH2Cl2/
diethyl ether, respectively, and full spheres of CCD area-
detector diffractometer data were measured (Bruker
AXS instrument, 2hmax ¼ 58°, x-scans, monochromatic
1
–red crystals of the product. Yield: 0.030 g (41%). H
3
NMR (CDCl3): d 8.95 (d, 2H, J ¼ 5:5 Hz, JPtH ꢃ 18
3
4
Hz, H6), 7.77 (td, J ¼ 8:0 Hz, J ¼ 1:2 Hz, H4), 7.47
3
ꢀ
(m, 6H, H3 and ortho-Tol), 7.36 (t, J ¼ 6:2 Hz, H5),
Mo Ka radiation, k ¼ 0:71073 A; T ca. 153 K) yielding
6.92 (d, 4H, 3J ¼ 8:4 Hz, meta-Tol), 6.63 (d, 4H,
3J ¼ 8:0 Hz, SeC6H4Cl), 6.36 (d, 4H, 3J ¼ 8:4 Hz,
SeC6H4Cl), 2.35 (s, 6H, Me). Anal. Calcd.: C, 47.28;
H, 3.31. Found: C, 47.26; H, 3.38%.
N
reflections, merging to N unique (Rint cited) after
ðtotalÞ
ÔempiricalÕ/multiscan absorption correction (proprietary
software), No with F > 4rðF Þ considered ÔobservedÕ and
used in the full-matrix least squares refinements, refining
anisotropic displacement parameter forms for the non-
hydrogen atoms, (x; y; zUiso H being included and con-
)
3.6. NMR studies
strained at estimated values. Conventional residuals R,
Rw (weights: ðr2ðF Þ þ 0:0004F 2Þꢀ1) on jF j are cited at
convergence. Neutral atom complex scattering factors
were employed within the Xtal 3.7 program system [10].
Pertinent results are given in Tables 1 and 2 and
Fig. 1(b), the latter showing 50% probability displace-
ment amplitudes for the non-hydrogen atoms, hydrogen
In a typical experiment for the determination of
equilibrium constants for the reaction of Scheme 1, a
sample of Pd(SeC6H4Cl)2Me(C6H4OMe)(bpy) (2)
(0.0040 g, 0.0052 mmol) was cooled to the required
temperature then dissolved in CD2Cl2 (600 ll). The
sample was kept at the required temperature for several
hours until equilibrium was reached. The concentration
of each compound was determined by integration, and
5% tolerance in integration was assumed (K ¼ 35408 ꢁ
7750 at )40 °C, 4628 ꢁ 950 at )35 °C, 2010 ꢁ 400 at )30
°C, 754 ꢁ 145 at )25 °C, 116 ꢁ 20 at )20 °C). In a typ-
ical experiment relating to the reactions of Eqs. (4)–(7),
a solution of (ClC6H4Se)2 (0.0040 g, 0.0105 mmol) in
CD2Cl2 (0.4 ml) was added to a solution of PdMeR
(dmpe) (R ¼ Me, Tol) (0.0105 mmol) in CD2Cl2 (0.2
ml). The sample was monitored by 1H and/or 31P NMR
spectroscopy to the completion of the reaction. To this
was added a second equivalent of (ClC6H4Se)2 (0.0040
g, 0.0105 mmol) and the reaction monitored to its
completion. NMR spectra (in CD2Cl2) of products are
listed above for complexes 5 and 6; Me–SeC6H4Cl: d
ꢀ
atoms having arbitrary radii of 0.1 A. Individual vari-
ations in procedure and difficulties are cited as ÔvariataÕ.
4. Crystal/refinement data
4.1. Pd(SeC6H4Cl)Me(dmpe) (5)
C13H23ClP2PdSe, M ¼ 462:1. Orthorhombic, space
group Pna21 ðC29v, No. 33), a ¼ 16:919ð3Þ, b ¼ 6:1734
3
ꢀ
ꢀ
ð9Þ, c ¼ 16:906ð3Þ A, V ¼ 1766 A . Dc ðZ ¼ 4Þ ¼ 1:738
g cmꢀ3. lMo ¼ 34 cmꢀ1; specimen: 0.20 ꢅ 0.17 ꢅ 0.14
mm; Tmin=max ¼ 0.88. 2hmax ¼ 75°; Nt ¼ 36023, N ¼ 4731
(Rint ¼ 0:051), No 2953; R ¼ 0:034, Rw ¼ 0:037.
Variata: Within the present space group, one of the
bidentate methylene groups is modelled as disordered
over a pair of sites, occupancies set at 0.5 after trial
refinement. ÔFriedelÕ data were preserved distinct, xabs
refining to 0.02(1).
3
3
7.35 (d, 2H, J ¼ 8:4 Hz), 7.23 (d, 2H, J ¼ 8:8 Hz),
2.34 (s, 3H, Me); Tol-SeC6H4Cl: d 7.40 (d, 2H, 3J ¼ 8:0
Hz), 7.31 (m) and 7.21 (m) overlapping, 7.13 (d, 2H,
3J ¼ 7:8 Hz), 2.33 (s, 3H, Me); Pd(SeC6H4Cl)
3
(C6H4OMe)(bpy) (3): d 9.06 (d, 1H, J ¼ 4:0 Hz, bpy),
8.10 (m, 2H, bpy), 8.00 (m, 2H, bpy), 7.92 (d, 1H,
3
3J ¼ 5:2 Hz, bpy), 7.69 (d, 2H, J ¼ 8:4 Hz, SeC6H4Cl
4.2. Pt(SeC6H4Cl)2(Tol)2(bpy) ꢂ 3CHCl3
or C6H4OMe), 7.45 (m, 1H, bpy), 7.35 (m, 1H, bpy
3
overlapping with other resonances), 7.21 (d, 2H, J ¼
(10 ꢂ 3CHCl3) ꢆ C39H33Cl11N2PtSe2, M ¼ 1272:7. Mo-
noclinic, space group C=c (C26h, No.15), a ¼ 24:345 ð3Þ,
3
8:4 Hz, SeC6H4Cl or C6H4OMe), 6.86 (d, 2H, J ¼ 8:4
3
ꢀ
Hz, SeC6H4Cl or C6H4OMe), 6.67 (d, 2H, J ¼ 8:0 Hz,
b ¼ 14:405ð2Þ, c ¼ 15:848ð2Þ A, b ¼ 127:032ð2Þ°,
3
ꢀ
SeC6H4Cl or C6H4OMe), 3.74 (s, 3H, OMe);
Pd(SeC6H4Cl)Tol(dmpe) (8): d 7.13 (m, 2H, Tol
or SeC6H4Cl), 6.89 (d(b), 2H, 3J ¼ 7:8 Hz, Tol or
SeC6H4Cl), 6.82 (d(b), 2H, 3J ¼ 6:8 Hz, Tol or
SeC6H4Cl), 2.20 (s, 3H, PdTol), 1.70 (m, 4H, CH2), 1.22
(d, 6H, JPH ¼ 10:4 Hz, PMe2), 1.05 (d, 6H, JPH ¼ 8:8
Hz, PMe2), 31P{1H} d 28.2 (d, JPP ¼ 20:9 Hz), 22.5 (d,
JPP ¼ 20:6 Hz).
V ¼ 4437 A . Dc (Z ¼ 4 f.u.) ¼ 1:905 g cmꢀ3. lMo ¼ 55
cmꢀ1; specimen: 0.35 ꢅ 0.12 ꢅ 0.12 mm; Tmin=max ¼ 0.57.
2hmax ¼ 50°; Nt ¼ 51575, N ¼ 3905 (Rint ¼ 0:11), No ¼
3260; R ¼ 0:059, Rw ¼ 0:072.
Variata: One of the solvent molecules was modelled
as disordered about a crystallographic 2-axis in the
present space group. The material presented as sub-
stantial, readily desolvating specimens, from which a