Organometallics
Article
Dichloro[N,N′-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene](3-
phenylinden-1-ylidene)(triisopropyl phosphite)ruthenium (2a). The
general procedure afforded 2a as an orange solid (460 mg, 0.48 mmol,
80%). 1H NMR (400 MHz, CD2Cl2): δ (ppm) 8.78 (d, 3JHH = 7.2 Hz,
1 H, H7), 7.57 (d, 3JHH = 7.2 Hz, 2 H, H9), 7.51 (dd, 3JHH = 7.5 Hz, 1
H, H9′), 7.29−7.44 (m, 7 H, H8′ H10 H11), 7.23 (dd, 3JHH = 7.3 Hz, 1
H, H5), 7.14 (dd, 3JHH = 7.2 Hz, 1 H, H6), 7.01 (d, 3JHH = 7.2 Hz, 1 H,
H4), 6.74 (d, 3JHH = 7.3, Hz, 1 H, H12′), 6.63 (dd, 3JHH = 7.7 Hz, 2 H,
H12′ H13′), 6.28 (s, 1 H, H2), 4.46 (sept, 3JHH = 6.3, 1 H, CH iPrNHC),
3.89−4.15 (m, 3 H, H4′a H4′b H3′a), 3.61−3.89 (m, 6 H, H3′b CH
ACKNOWLEDGMENTS
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We gratefully acknowledge the EC (CP-FP 211468-2 EUMET)
and the Royal Society (University Research Fellowship to
C.S.J.C.) for funding.
REFERENCES
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i
3
i
iPrNHC CH Prphosphite), 3.00 (sept, JHH = 7.0 Hz, 1 H, CH PrNHC),
1.60−1.64 (m, 6 H, CH3 iPrNHC), 1.54 (d, JHH = 6.3 Hz, 3 H, CH3
3
iPrNHC), 1.28−1.29 (m, 3 H, CH3 iPrNHC), 1.20−1.24 (m, 6 H, CH3
3
3
iPrNHC), 0.95 (d, JHH = 6.0 Hz 9 H, CH3phosphite), 0.85 (d, JHH = 6.7
3
Hz, 3 H, CH3phosphite), 0.73 (d, JHH = 5.9 Hz 9 H, CH3phosphite), 0.44
(d, JHH = 6.7 Hz, 3 H, CH3phosphite). 13C{1H} NMR (CD2Cl2, 101
3
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2
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146.8 (s, CIV), 143.5 (s, CIV), 143.4 (s, CIV), 141.3 (s, CIV), 140.7 (s,
CIV), 137.7 (s, C2), 136.9 (s, CIV), 136.8 (s, CIV), 135.9 (s, CIV), 131.5
(s, C7), 130.2 (s, C11 C13′), 129.5 (s, C5), 128.9 (s, C6), 128.2 (C9′),
127.1 (C9), 125.6 (s, CH), 125.3 (s, CH), 124.7(s, CH), 124.0 (s,
C12), 117.0 (s, C4), 69.2 (d, 2JCP = 4.3 Hz, CH iPrphosphite) 55.2 (d, 4JCP
= 5.4 Hz, C4′), 55.0 (d, 4JCP = 3.5 Hz, C3′), 30.2 (s, CH iPrNHC), 29.3
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(s, CH PrNHC), 28.8 (s, CH PrNHC), 27.3 (s, CH PrNHC), 26.8−27.3
(m, CH PrNHC) 23.6−24.4 (m, CH PrNHC CH Prphosphite). 31P{1H}
NMR (CD2Cl2, 121 MHz): δ (ppm) 116.65 (s). Anal. Calcd for
C51H69Cl2N2O3PRu: C, 63.74; H, 7.24; N, 2.91. Found: C, 63.73; H,
7.46; N, 3.02.
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Dichloro[N,N′-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene](3-
phenylinden-1-ylidene)(triethyl phosphite)ruthenium (2b). The
general procedure afforded 2b as an orange solid (358 mg, 0.39
mmol, 65%). 1H NMR (300 MHz, C6D6): δ (ppm) 9.41 (d, 3JHH = 7.2
3
Hz, 1 H, H7), 7.66 (d, JHH = 7.2 Hz, 2 H9) 7.16 (br m, 9 H, HAr),
6.51−6.88 (m, 4 H, HAr), 4.63 (br s, 1 H, CH2 NHC), 4.06 (br s, 1 H,
CH2 NHC), 3.12−3.94 (m, 12 H, H3 H4 CH iPr CH2phosphite), 1.85 (br
s, 9 H, CH3phosphite), 0.53−1.49 (m, 24 H, CH3 iPr). 13C{1H} NMR
(101 MHz, CD2Cl2): δ (ppm) 301.0 (d, 2JCP = 20.8 Hz, C1), 217.7 (d,
2JCP = 131.7 Hz, C1′), 150.5 (s, CIV), 143.5 (s, CIV), 143.4 (s, CIV),
141.1(s, CIV), 140.7 (s, CIV), 137.7 (s, C2), 136.8(s, CIV), 136.5 (s,
CIV), 135.6 (s, CIV), 131.2 (s, C7), 130.1 (s, C9′), 130.1(s, C13′), 129.6
(s, C5), 128.9 (s, 2C, C10), 128.8 (s, C6), 128.3 (s, C11), 127.1 (s, C9),
2
124.7 (s, C8′), 124.0 (s, C12′) 117.2 (s, C4), 60.8 (d, JCP = 3.0 Hz,
CH2phosphite), 55.2 (d, 4JCP = 5.5 Hz, C4′), 55.0 (d, 4JCP = 3.4 Hz, C4′),
27.2 (s, CH3 NHC), 27.0 (s, CH3 NHC), 23.7 (s, CH3 NHC), 16.1
(d, 3JCP = 6.4 Hz, CH3phosphite). 31P{1H} NMR (121 MHz, CD2Cl2): δ
(ppm) 123.7 (s). Anal. Calcd for C48H63Cl2N2O3PRu: C, 62.73, H,
6.91, N, 3.05. Found: C, 62.59, H, 6.84, N, 3.22.
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ASSOCIATED CONTENT
* Supporting Information
Text, tables, figures, and a CIF file giving procedures for
catalysis, NMR spectra of complexes and catalysis products,
procedure and NMR spectra for the isomerization of 2b, crystal
data and structure refinement details for 2a, calculations for %
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Bur, and topographical steric maps. This material is available
AUTHOR INFORMATION
Corresponding Author
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Present Address
§Institut des Biomolec
́
ules Max Mousseron, UMR 5247,
́
Montpellier II, Place E. Bataillon, 34095 Montpellier
Universite
Cedex 5, France.
(9) Paek, S.-M. Molecules 2012, 17, 3348.
Notes
(10) (a) Vorfalt, T.; Leuthaußer, S.; Plenio, H. Angew. Chem.- Int. Ed.
̈
The authors declare no competing financial interest.
2009, 48, 5191. (b) Peeck, L. H.; Plenio, H. Organometallics 2010, 29,
G
dx.doi.org/10.1021/om4004362 | Organometallics XXXX, XXX, XXX−XXX