P.A. 6an der Schaaf et al. / Journal of Organometallic Chemistry 606 (2000) 65–74
73
3.40 (m, 2, ꢀCHCH2CH2); 3.22 (s, 3, 6-methyl); 2.93
(m, 2, ꢀCHCH2CH2); 2.65 (m, 3, P(CHMe2)3); 1.4 (m,
18, P(CHMe2)3). 31P-NMR: l 42.5.
reflections (Rint=0.063), 3116 were considered ob-
served [I\2|(I)], final R=0.0341, wR2=0.0476 (ob-
served data), goodness of fit 0.698, residual density
−3
,
max./min. 0.341 (near the Ru atom) /−0.340 e A
.
4.14. Synthesis of 4c
Absorption coefficient v=0.802 mm−1; no correction
for absorption was applied. Intensity data were col-
lected at r.t. on a Stoe image plate diffraction system
using Mo Ka graphite monochromated radiation. Im-
age plate distance 70 mm, scans 0–200°, step D=
The reaction was performed in a similar way as
described for 4a. Using 2-(3-butenyl)-5-methylpyridine
(ligand 3c) the desired product was obtained as a brown
1
,
powder in 61% yield. H-NMR: l 19.44 (dt, 1, carbene-
1°, 2q range 3.27–52.1°, dmax–dmin=12.45–0.8 1 A.
3
H, JPH=11.9 Hz); 8.47, 7.40, 7.08 (3, py-H); 3.53 (m,
The structure was solved by direct methods using the
program SHELXS-97 [19]. The refinement and all further
calculations were carried out using SHELXL-97 [20]. All
of the H-atoms were included in calculated positions
and treated as riding atoms using SHELXL-97 default
parameters. The non-H atoms were refined anisotropi-
cally, using weighted full-matrix least-squares on F2.
2, ꢀCHCH2CH2); 2.50 (m, 3, P(CHMe2)3); 2.39 (m, 2,
ꢀCHCH2CH2); 2.26 (s, 3, 5-methyl); 1.4 (m, 18,
P(CHMe2)3). 31P-NMR: l 44.0.
4.15. Synthesis of 4d
The reaction was performed in a similar way as
described for 4a. Using 2-(3-butenyl)-4-methylpyridine
(ligand 3d) the desired product was obtained as a
4.19. Crystal structure of 4a
1
brown powder in 65% yield. H-NMR: l 19.48 (dt, 1,
Suitable crystals of 4a were grown from a hot toluene
solution as dark red blocks. C17H30Cl2NPRu, triclinic,
3
carbene-H, JPH=11.8 Hz); 8.57, 7.24, 7.07 (3, py-H);
(
3.53 (m, 2, ꢀCHCH2CH2); 2.60 (m, 3, P(CHMe2)3);
2.46 (m, 2, ꢀCHCH2CH2); 2.36 (s, 3, 4-methyl); 1.4 (m,
18, P(CHMe2)3). 31P-NMR: l 42.8.
space group, P1 a=8.2949(5), b=8.8564(5), c=
,
15.7133(8) A, h=92.908(4), i=102.328(6), k=
114.821(5)°, Z=2, calc=1.483 6805
D
g
cm−3
,
reflections collected, 3754 independent reflections
(Rint=0.0249), 3412 were considered observed [I\
2|(I)], final R=0.0249, wR2=0.0567 (observed data),
4.16. Synthesis of 4e
The reaction was performed in a similar way as
described for 4a. Using 2-(3-butenyl)-3-methylpyridine
(ligand 3e) the desired product was obtained as a brown
goodness of fit 1.101, residual density max./min. 0.373/
−3
,
−0.379
e
A
. Absorption coefficient v=1.116
mm−1; no correction for absorption was applied. In-
tensity data were collected at r.t. on a Stoe AED2
4-circle diffractometer using Mo Ka graphite
monochromated radiation, using 2q/ꢀ scans in the
range 4–51° in 2q. The structure was solved by direct
methods using the program SHELXS-97 [19]. The refine-
ment and all further calculations were carried out using
SHELXL-97 [20]. The H-atoms of the organic ligand
were located from difference maps and refined isotropi-
cally. The H-atoms of the tris(isopropyl)phosphine lig-
and were included in calculated positions and treated as
riding atoms using SHELXL-97 default parameters. The
non-H atoms were refined anisotropically, using
weighted full-matrix least-squares on F2.
1
powder in 60% yield. H-NMR: l 19.45 (dt, 1, carbene-
3
H, JPH=11.5 Hz); 8.58, 7.44, 7.08 (3, py-H); 3.53 (m,
2, ꢀCHCH2CH2); 2.97 (m, 2, ꢀCHCH2CH2); 2.55 (m, 3,
P(CHMe2)3); 2.34 (s, 3, 3-methyl); 1.4 (m, 18,
P(CHMe2)3). 31P-NMR: l 44.6.
4.17. Synthesis of 4f
The reaction was performed in a similar way as
described for 4a. Using 2-(3-butenyl)-5-methylpyridine
(ligand 3f) the desired product was obtained as a brown
1
powder in 55% yield. H-NMR: l 19.75 (dt, 1, carbene-
3
H, JPH=13.1 Hz); 6.85, 6.82 (2s, 2, py-H); 3.29 (m, 2,
ꢀCHCH2CH2); 3.11 (s, 3, 6-methyl); 2.86 (m, 2,
ꢀCHCH2CH2); 2.61 (m, 3, P(CHMe2)3); 2.24 (s, 3,
4-methyl); 1.4 (m, 18, P(CHMe2)3). 31P-NMR: l 42.3
5. Supplementary material
4.18. Crystal structure of 2a
The crystallographic CIF files have been deposited
with the Cambridge Crystallographic Data Center (de-
position numbers: CCDC 138602 (2a); CCDC 138603
(4a)). Copies of this information may be obtained free
of charge from: The Director, CCDC, 12 Union Road,
Cambridge, CB2 1EZ, UK (Fax: +44-1223-336-033;
e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).
Suitable crystals of 2a were grown from a hot toluene
solution as very small dark-red rods. C25H48Cl2P2RuS,
(
triclinic, space group, P1, a=8.7596(7), b=9.7255(9),
,
c=18.7729(18) A, h=76.75(1), i=81.61(1), k=
3
,
75.19(1)°, V=1498.5(2) A , Z=2, Dcalc=1.362 g
cm−3, 11 668 reflections collected, 5358 independent