4064 Organometallics, Vol. 28, No. 14, 2009
Delaude et al.
3
para-CH3), 2.53 (sept, 1 H, p-cym CH(CH3)2), 5.46 (d, 3JHH
=
CDCl3): δ 1.03 (d, JHH = 6.8 Hz, 6 H, p-cym CH(CH3)2),
1.30 (d, 3JHH=6.4 Hz, 12 H, SIDip CH(CH3)2), 1.34 (d, 3JHH
6.4 Hz, 12 H, SIDip CH(CH3)2), 2.04 (s, 3 H, p-cym CH3), 2.43
(sept, 3JHH=6.8 Hz, 1 H, p-cym CH(CH3)2), 2.94 (sept, 3JHH
6.4 Hz, 4 H, SIDip CH(CH3)2), 4.42 (s, 4 H, CH2N), 5.40
3
5.6 Hz, 2 H, p-cym CHar), 5.65 (d, JHH=5.6 Hz, 2 H, p-cym
CHar), 7.03 (s, 4 H, meta-CH), 7.57 (s, 2 H, dCHN) ppm.
13C NMR (100 MHz, CDCl3): δ 17.6, 19.3, 21.4, 22.6, 32.3,
86.4, 86.6, 106.7, 106.8, 126.3, 130.1, 130.4, 136.8, 142.3, 212.4
=
=
3
3
(CS2) ppm. IR (KBr): ν 3171, 3145, 2962, 2922, 1608, 1552,
(d, JHH =6.0 Hz, 2 H, p-cym CHar), 5.57 (d, JHH =6.0 Hz,
2 H, p-cym CHar), 7.25 (d, 3JHH=7.6 Hz, 4 H, meta-CH), 7.49
h
1485, 1384, 1233, 1025, 842, 720, 558 cm-1. UV/vis (MeCN):
λ (ε) 197 (81 900), 313 (10 700), 396 (4000), 518 (3300) nm
(M-1 cm-1). Anal. Calcd for C32H38ClF6N2PRuS2 (796.28):
C, 48.27; H, 4.81; N, 3.52; S, 8.05. Found: C, 48.14; H, 4.59; N,
3.71; S, 8.24.
(t, JHH=7.6 Hz, 2 H, para-CH) ppm. 13C NMR (100 MHz,
3
CDCl3): δ 19.6, 22.8, 23.8, 25.8, 29.6, 32.2, 54.1, 87.8, 87.9,
105.9, 109.2, 125.2, 125.6, 130.0, 131.8, 146.4, 153.4, 211.8 (CS2)
ppm. IR (KBr): ν 3175, 2968, 2928, 2870, 1591, 1549, 1504, 1466,
1445, 1389, 1360, 1323, 1285, 1083, 1058, 844, 805, 758, 687,
558 cm-1. Anal. Calcd for C38H52ClF6N2PRuS2 (882.45): C,
51.72; H, 5.94; N, 3.17; S, 7.27. Found: C, 51.23; H, 5.94; N,
3.42; S, 7.05.
X-ray Crystal Structure Determination. Data were collected at
room temperature on a Gemini diffractometer (Oxford Diffrac-
tion Ltd.) equipped with a Ruby CCD detector using an
Enhance (Mo) X-ray source. Data collection program: CrysAlis
CCD (Oxford Diffraction Ltd.), data reduction: CrysAlis
RED (Oxford Diffraction Ltd.), structure solution: SHELXS,
structure refinement (on F2): SHELXL-97,44 data analysis:
PLATON.45 A multiscan procedure was applied to correct for
absorption effects. Hydrogen atom positions were calculated
and refined isotropically using a riding model. Disorder of the
PF-6 ion was refined.
h
[RuCl(p-cymene)(IDip CS2)]PF6 (6): dark blue, microcrys-
3
talline powder (0.24 g, 69% yield). 1H NMR (400 MHz, CDCl3):
3
δ 1.06 (d, JHH =5.6 Hz, 6 H, p-cym CH(CH3)2), 1.19-1.24
(m, 24 H, IDip CH(CH3)2), 2.09 (s, 3 H, p-cym CH3), 2.32 (sept,
3JHH=6.0 Hz, 4 H, IDip CH(CH3)2), 2.48 (sept, 3JHH=6.6 Hz,
1 H, p-cym CH(CH3)2), 5.41 (d, JHH = 5.0 Hz, 2 H, p-cym
3
CHar), 5.58 (d, 3JHH=5.0 Hz, 2 H, p-cym CHar), 7.36 (d, 3JHH
=
6.8 Hz, 4 H, meta-CH), 7.62 (t, 3JHH=7.2 Hz, 2 H, para-CH),
7.71 (s, 2 H, dCHN) ppm. 13C NMR (100 MHz, CDCl3): δ
19.5, 22.8, 23.1, 24.9, 29.6, 32.3, 81.1, 87.3, 106.4, 107.5, 125.6,
127.7, 130.1, 132.8, 136.8, 145.2, 211.8 (CS2) ppm. IR (KBr):
ν 3175, 2966, 2930, 2872, 1549, 1471, 1389, 1368, 1207, 1061,
h
1010, 843, 804, 756, 722, 558 cm-1. UV/vis (MeCN): λ (ε)
193 (88 000), 238 (22 800) shoulder, 328 (11 600), 550 (4200)
nm (M-1 cm-1). Anal. Calcd for C38H50ClF6N2PRuS2 (880.45):
C, 51.84; H, 5.72; N, 3.18; S, 7.28. Found: C, 51.09; H, 5.71; N,
3.42; S, 7.01.
Crystal Data for [RuCl(p-cymene)(IMes CS2)]PF6 (5): dark
3
purple crystals (from MeCN), triclinic, P1, a=8.126(1) A, b=
14.560(1) A, c=16.441(1) A, R=77.9(1)°, β=80.5(1)°, γ=77.2
(1) °, V=1841.0(1) A3, Z=2, Fcalc=1.436 g cm-3, F000=812,
λ(Mo KR)=0.71073 A, θmax =28.20°, 52 973 total measured
reflections, 8363 independent reflections (Rint =0.0288), 5698
observed reflections (I > 2σ(I)), μ = 0.710 mm-1, 451 para-
meters, R1 (all data) = 0.0554, R1 (observed data) = 0.0340,
[RuCl(p-cymene)(SIMes CS2)]PF6 (7): dark purple, micro-
3
1
crystalline powder (0.22 g, 69% yield). H NMR (400 MHz,
CD2Cl2): δ 0.96 (d, 3JHH=6.8 Hz, 6 H, p-cym CH(CH3)2), 2.09
(s, 3 H, p-cym CH3), 2.33 (s, 18 H, mesityl CH3), 2.40 (m, 1 H,
p-cym CH(CH3)2), 4.32 (s, 4 H, CH2N), 5.44 (d, 3JHH=6.0 Hz,
2 H, p-cym CHar), 5.63 (d, 3JHH=6.0 Hz, 2 H, p-cym CHar), 6.98
(s, 4 H, meta-CH) ppm. 13C NMR (100 MHz, CD2Cl2): δ 17.9,
19.1, 21.0, 22.4, 32.2, 51.0, 86.1, 86.8, 107.4, 107.6, 130.1, 130.3,
S=GooF=1.049, Δ/s.u.=0.002, residual Fmax=0.872 e A-3
min=-0.349 e A-3
,
F
.
135.8, 141.3, 156.2, 213.1 (CS2) ppm. IR (KBr): ν 2963, 2922,
h
Acknowledgment. We thank Ms. A. Richel and Ms. P.
ꢀ
Wrzesniak for the ATRP catalytic tests and Mrs B.
Norberg for the XRD analyses.
1610, 1559, 1511, 1466, 1382, 1355, 1291, 1213, 1088, 1032, 842,
741, 689, 575, 558 cm-1. UV/vis (MeCN): λ (ε) 195 (85 700), 513
(2400) nm (M-1 cm-1). Anal. Calcd for C32H40ClF6N2PRuS2
(798.30): C, 48.15; H, 5.05; N, 3.51; S, 8.03. Found: C, 48.08; H,
4.98; N, 3.69; S, 8.02.
Supporting Information Available: CIF file with crystallo-
graphic data for complex 5. This material is available free of
[RuCl(p-cymene)(SIDip CS2)]PF6 (8): dark brown, micro-
crystalline powder (0.31 g, 89% yield). H NMR (400 MHz,
3
1
(44) Sheldrick, G. M. SHELXL-97, Program for the Refinement of
€
(45) Speck, A. L. PLATON, A Multipurpose Crystallographic Tool;
Utrecht University: Utrecht (The Netherlands), 2005.
€
Crystal Structures; University of Gottingen: Gottingen (Germany), 1997.