Organometallics
ARTICLE
JHꢀH = 7.6, JHꢀRh = 2.1, 1H, η2-CH2dCHPh), 4.48, 3.60, 3.16, and 2.44
parameters ΔHq and ΔSq were obtained by a linear least-squares fit of the
Eyring plot. Errors were computed by published methods.26
(allsept,JHꢀH =6.4, 4H, CHMe),2.71(ddd,JHꢀH =7.6,JHꢀP =2.5,JHꢀRh
=
2.1, 1H, η2-CH2=CHPh), 2.56 (ddd, JHꢀH = 9.8, JHꢀP = 9.8, JHꢀRh = 2.1,
1H, η2- CH2dCHPh), 1.56, 1.50, 1.42, 1.39, 1.12, 1.10, 1.04, and 1.01 (all
d, JHꢀH =6.4, 24H,CHMe). 13C{1H} NMR(100.2MHz, C6D6, 293K):δ
186.6 (dd, JCꢀP = 138.7, JCꢀRh = 47.5, RhꢀCIPr), 148.6, 148.3, 146.9, and
146.7 (all s, Cq-IPr), 144.9 (dd, JCꢀP = 2.4, JCꢀRh = 2.4, Cipso-sty), 137.4 and
’ ASSOCIATED CONTENT
S
Supporting Information. A CIF file giving crystal data
b
and processing parameters for compound 2 and figures giving
NOE NMR experiments. This material is available free of charge
137.2 (both s, CqN), 135.4 (d, JCꢀP = 11.0, CHo-PPh), 135.3 (d, JCꢀP
36.4, CqP), 130.0, 129.6, 124.9, 124.2, 123.8, and 122.8 (all s, CHph-Ipr),
128.2 (s, CHo-sty), 127.9 (s, CHm-sty), 127.2 (s, CHp-PPh), 126.8 (d, JCꢀP
=
=
8.6, CHm-PPh), 125,0 (s, CHp-sty), 123.7 and 123.3 (both s, dCHN), 58.0
(d, JCꢀRh = 14.8, η2-CH2dCHPh), 34.0 (dd, JCꢀRh = 14.8, JCꢀP = 3.7, η2-
CH2dCHPh), 29.2, 29.0, 28.8, and 28.3 (both s, CHMe), 27.1, 26.5, 26.3,
25.8, 23.0, 22.7, 22.1, and 21.9 (all s, CHMe). 31P{1H} NMR (202.5 MHz,
C6D6, 293 K): δ 32.3 (d, JPꢀRh = 122.9).
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: rcastar@unizar.es.
Preparation of RhCl{η3-CH2dCH(OEt)}(IPr)PPh3 (5). This
complex was prepared as described for 4, starting from 2 (100 mg, 0.12
mmol) and ethyl vinyl ether (115 μL, 2.06 mmol). Yield: 96 mg (93%).
Anal. Calcd for C49H59N2ClOPRh: C, 68.32; H, 6.90; N, 3.24. Found:
’ ACKNOWLEDGMENT
Financial support from the Ministerio de Ciencia e Innovaciꢀon
(MICINN/FEDER) of Spain (Project CTQ2010-15221), the
Diputaciꢀon General de Aragꢀon (E07), the ARAID Foundation
under the program “Jꢀovenes Investigadores”, and CONSOLIDER
INGENIO-2010, Projects MULTICAT (CSD2009-00050) and
Factoría de Crystalizaciꢀon (CSD2006-0015), are gratefully ac-
knowledged. R.C. thanks the CSIC and the European Social
Fund for his Research Contract in the framework of the “Ramꢀon y
Cajal” Program.
1
C, 67.99; H, 6.72; N, 2.98. H NMR (300 MHz, C6D6, 293 K): δ
7.6ꢀ7.0 (24H, HPh), 6.47 and 6.45 (both d, JHꢀH = 2.0, 2H, =CHN),
5.44 {m, 1H, η2-CH2dCH(OEt)}, 4.47, 3.44, 3.34, and 2.26 (all sept,
JHꢀH = 6.4, 4H, CHMe), 3.56 and 2.72 (both m, CH3CH2O), 1.84, 1.47,
1.39, 1.15, 1.13, 1.00, 0.96, and 0.92 (all d, JHꢀH = 6.4, 24H, CHMe),
1.63 and 1.44 {both m, 2H, η2-CH2dCH(OEt)}, 0.36 (t, JHꢀH = 6.8,
3H, CH3CH2O). 13C{1H} NMR (75.4 MHz, C6D6, 293 K): δ 186.8,
(dd, JCꢀP = 135.7, JCꢀRh = 49.0, RhꢀCIPr), 148.5, 148.3, 145.5, and
145.1 (all s, Cq-IPr), 137.3 and 137.1 (both s, CqN), 135.1 (d, JCꢀP
=
35.7, CqP), 132.1 (d, JCꢀP = 8.8, CHPPh), 129.9, 129.7, 128.4, 128.2,
127.2, 127.1, 124.9, and 123.4 (all s, CHPh), 124.7 and 123.2 (both
s, dCHN), 103.6 {d, JCꢀRh = 16.1, η2-CH2dCH(OEt)}, 65.8 (s,
CH3CH2O), 29.3, 29.0, 28.4, and 28.4 (both s, CHMe),), 27.1, 26.2,
’ DEDICATION
†Dedicated to Professor Christian Bruneau on the occasion of his
60th birthday.
25.8, 25.6, 23.5, 23.0, 22.7, and 22.3 (all s, CHMe), 26.5 (dd, JCꢀRh
=
14.8, JCꢀP = 2.2, η2-CH2dCH(OEt)), 13.9 (s, CH3CH2O). 31P{1H}
NMR (121.5 MHz, C6D6, 293 K): δ 34.8 (d, JPꢀRh = 131.6).
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X-ray Structure Determination of RhCl(dCHPh)(IPr)PPh3
(2). A green prismatic crystal of 2 (0.07 ꢁ 0.12 ꢁ 0.14 mm) suitable for
X-ray diffraction was obtained by slow diffusion of n-hexane into a
concentrated THF solution of the complex at 253 K. Intensity data were
collected at low temperature (100(2) K) on a single-axis HUBER
diffractometer at BM16 of the ESRF synchrotron, equipped with a
Si111 double-crystal monochromator (λ = 0.737 80 Å) using wide
frames (1° in ϕ). Two sets of data at different orientations of the crystal
(changing a pseudo-k angle by ∼40°) were measured to ensure data
completeness. Cell parameters were refined from the observed setting
angles and detector positions of strong reflections (78 866 reflections,
2θ < 66.7°). Data were corrected for Lorentz and polarization and for
absorption effects, scaled, and merged using the SORTAV program.24
The structure was solved by Patterson methods and completed by
successive difference Fourier syntheses (SHELXS-86).25 Refinement, by
full-matrix least squares on F2 with SHELXL97,25 was carried out
including isotropic and subsequent anisotropic displacement parameters
for all non-hydrogen atoms. Hydrogen atoms were included from
observed positions and refined riding on their parent carbon atoms.
Final agreement factors were R1 = 0.0542 (11 427 reflections, I > 2σ(I)),
wR2 = 0.1543 (12 781 unique reflections), and GOF = 1.088. All the
highest electronic residuals (smaller than 1.1 e/Å3) were observed in
close proximity of the Rh metal and have no chemical sense. Atomic
scattering factors, corrected for anomalous dispersion, were used as
implemented in the refinement programs.25
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Determination of Rotational Barriers. Full line-shape analysis
of the dynamic 1H NMR spectra of 2 and 3 were carried out using the
program gNMR (Cherwell Scientific Publishing Limited). The transverse
relaxation time, T2, was estimated at the lowest temperature. Activation
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dx.doi.org/10.1021/om2005782 |Organometallics 2011, 30, 5208–5213