10.1002/chem.201703313
Chemistry - A European Journal
1
0.139 mmol, 51%). H-NMR (400 MHz, CD2Cl2): 7.13-7.09 (m,
The authors declare no conflict of interests.
2H), 6.52-6.49 (m, 2H), 3.20 (s, 3H), 3.15 (s, 3H), 3.00 (s, 3H),
1.75 (s, 3 H), 1.64 (s, 6H) ppm; 13C-NMR (100 MHz, CD2Cl2):
300.3, 196.4, 161.3, 138.1, 132.9, 124.3 (q, JCF = 289.08 Hz),
124.1 (q, JCF = 287.31 Hz), 115.6, 114,7. 114.2, 106.9, 106.4,
84.3-82.4 (m)*, 55.9, 39.7, 34.9, 37.1, 20.1, 19.8 ppm; 19F-NMR
(377 MHz, C6D6): -77.67 (s, 6F), -77.80 – -77.88 (m, 6F), -
78.24 – -78.27 (m, 6F) ppm; EA calcd.: C27H22F18MoN4O4: C,
35.86; H, 2.45; N, 6.19. Found: C, 35.73; H, 2.73; N, 5.89.
Crystals suitable for single crystal X-ray diffraction were
obtained by over layering an almost saturated solution of Mo-3
in diethyl ether with pentane and allowing to stand the solution at
-40°C overnight. *The expected septets are reported as a
multiplet due to strong overlapping.
Keywords: N-heterocyclic carbenes • alkylidynes • molybdenum
• metathesis • alkynes
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p-OMe-C6H4CMo(1,3-diisopropylimidazol-2-
ylidene)(OCMe(CF3)2)3 (Mo-4)
In a glove box, V and 1,3-diisopropylimidazol-2-ylidene 4 (36 mg,
0.24 mmol) were dissolved in toluene in a Schlenk tube
equipped with a magnetic stir bar. Both mixtures were cooled to
-40°C. The solution of 4 was slowly added to the solution of V.
The reaction mixture was removed from the glove box and
stirred 20 min at room temperature, then for 3 h at 40°C. In
course of the reaction, a color change from brown to red was
observed. The reaction mixture was concentrated in vacuo and
brought back into the glove box. The remaining solid was
crystallized from diethyl ether/pentane to give the product as a
brown solid (36 mg, 0.24 mmol). The reaction mixture was
stirred a 40°C for 3 h. The product was obtained as a brown
1
solid (149 mg, 0.164 mmol, 69%). H-NMR (400 MHz, C6D6):
7.35-7.33 (m, 2H), 6.54-6.52 (m, 2H), 6.21-6.20 (m, 2H), 5.36
(sept., 3JHH = 6.56 Hz, 1H), 4.17 (sept., 3JHH = 6.52 Hz, 1H), 3.19
3
(s, 3H), 1.90 (s, 3H), 1.74 (s, 6H), 1.05 (d, JHH = 6.60 Hz, 6H),
3
1.02 (d, JHH = 6.68 Hz, 6H) ppm; 13C-NMR (100 MHz, CD2Cl2):
298.2, 186.1, 160.4, 138.2, 132.1, 124.68 (q, JCF = 288.64 Hz),
124.47 (q, JCF = 289.46 Hz), 124.32 (q, JCF = 290.22 Hz), 117.3,
2
2
116.6, 113.6, 83.5 (sept., JCF = 28.57 Hz)*, 82.91 (sept., JCF
=
28.87 Hz)*, 55.8, 53.1, 52.9, 24.0, 23.13, 23.08, 20.0, 19.4 ppm;
19F-NMR (377 MHz, C6D6): -76.12 – -76.19 (m, 6F), -76.30 – -
76.34 (m, 6F), -76.87 (s, 6F) ppm; EA calcd.: C29H32F18MoN2O4:
C, 38.26; H, 3.54; N, 3.08. Found: C, 38,17; H, 3.60; N, 3.24.
Dark brown crystals suitable for single crystal X-ray diffraction
were obtained by over layering an almost saturated solution of
Mo-4 in diethyl ether with pentane storing the solution at -40°C
overnight. *Terminal signals of the septet are not observable.
Acknowledgements
We gratefully acknowledge the Federal Ministry of Education
and
Research,
Germany
for
financial
support
(Deutschlandstipendium to M.K.). J.M. and J.K. were financially
supported by the German Research Foundation (DFG) within
the Cluster of Excellence in Simulation Technology (EXC 310/2)
at the University of Stuttgart.
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Conflict of interest
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