P. Lipovská et al. / Journal of Fluorine Chemistry 191 (2016) 14–22
21
F = 3 Hz, 3F), À129.2 + (À131.3) + (À131.3) + (À131.4) + (À131.6)
7.35 (tm, 1H, ArH), 17.17 + 17.21 + 17.22 + 17.26 + 17.27 (5 Â bs, 1H,
3
(5 Â m, 1F). 13C NMR (100.58 MHz, CD2Cl2):
d
19.8 (bs, 4C,
Ru = CH) ppm. 19F NMR (282,23 MHz, CD2Cl2):
d
À81.1 (t, JFÀ
Ar'CH3-o), 20.1 + 20.1 (2 Â s, 2C, Ar'CH3-p), 20.8 (s, 2C, OCH
(CH3)2), 52.3 (m, 2C, CH2N), 52.9 + 52.9 + 53.0 (3 Â s, 1C, OCH3),
74.9 + 75.0 (2 Â s, 1C, OCH(CH3)2), 106–120 (m, 22C, CF3, CF2, CF),
114.2 (s, 1C, CArHCArOiPr), 122.0 + 122.3 + 122.6 (3 Â s, 1C, CArH),
F = 8 Hz, 6F, CF3), À81.6 (m, 6F, CF3CF2CF2), À83.9–(À85.5) (m, 2F,
CF3CF2CFF), À86.1–(À87.2) (m, 2F, CF3CF2CFF), À114.9 (m, 4F,
CF2CH2), À122.1 (m, 4F, CF2CF2CH2), À123.1 (m, 4F, CF2CF2CF2CH2),
À124.1 (m, 4F, CF3CF2CF2), À126.4 (m, 4F, CF3CF2CF2), À129.3 (dm,
2JH-F = 60 Hz, 2F, CHF), À129.8 (m, 4F, CF3CF2CF2O) ppm. 13C NMR
123.3 + 123.7 + 124.1 (s, 1C,
CArH), 129.4 + 129.4 + 129.5 + 129.5
(4 Â s, 4C, CAr'H), 129.6 + 129.7 + 129.7 (3 Â s, 1C, CArH), 134.6 (m,
(100,58 MHz, CD2Cl2):
d
18.90 + 19.50 (2 Â s, 4C, Ar'CH3-o), 20.60
2C, Ar'CH3), 139.3 (bs, 4C, Ar'CH3), 139.4 (m, 2C, Ar'N),
C
C
C
(bs, 2C, OCH(CH3)), 21.30 (s, 2C, p-CH3), 25.69 (m, 2C, CF2CH2CH2),
28.13 (t, 2JCÀF = 21 Hz, 2C, CF2CH2CH2), 69.14 (s, 2C, CF2CH2CH2CH),
75.00 (m, 1C, OCH(CH3)), 96.58 + 99.05 (2 Â m, 2C, CHF), 107.08–
119.69 (m, 18C, CF3, CF2), 111.52 (s, 1C, CArH), 122.36 (s, 1C, CArH),
123.45 (s, 1C, CArH), 130.05 (s, 4C, CAr'H), 130.45 (s, 1C, CArH), 133.41
(bs, 2C, CAr'CH3), 138.82 + 139.13 + 139.28 (3 Â s, 4C, CAr'CH3), 140.19
(s, 2C, CAr'N), 143.26 (m, 1C, CArCH = Ru), 153.08 (m, 1C, CArOiPr),
163.65 + 163.84 (2 Â s, 2C, COO), 214.85 (s,1C, Ru = CNN), 313.53 (m,
1C, Ru = CH) ppm. MS (ESI), m/z (%) 1793 [M+Na]+ (48); 1509 [M-
(C5HF8O3)]+ (51); 1247 [M-(2 Â C5HF8O3)]+ (100); 999 (28). HRMS
(ESI): calcd. for C57H46F42N2NaO7Ru ([M+Na]+) 1793.1570, found
1793.1571.
142.7 + 143.0 + 143.2 (3 Â s, 1C, CArCH = Ru), 153.3 + 153.5 + 153.6
(3 Â s, 1C, CArOiPr), 162.3 (m, 2C, COO), 210.3 + 210.4 (2 Â s, 1C,
NCN), 315.2 (m, 1C, CH = Ru) ppm. MS (ESI+) m/z (%): 929.2 [M+Na]+
(100), 731.2 (59), 441.3 (88). HRMS (ESI+): [M+Na]+ calcd. for
C39H44F8N2NaO7Ru 929.1956, found 929.1965.
4.11. [4,5-Bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-1,3-bis
(2,4,6-trimethylphenyl)-imidazolidin-2-ylidene](2-
isopropoxybenzylidene)bis[perfluoro(2-methyl-3-oxahexanoyl)-oxy]
ruthenium(IV) (2a)
According to the general procedure, silver salt 3a (36 mg,
0.083 mmol) and complex 5 (HG2, 14 mg, 0.011 mmol) gave the
target complex 2a (19.4 mg, 97%, deep violet wax). 1H NMR
4.13. Study of catalytic activity. general procedure
(299.97 MHz, CD2Cl2):
d
0.82–0.93 (m, 3H, (CH3)CH(CH3)O), 0.94–
An NMR tube was charged with catalyst (5.0 mmol, 5 mol%) and
1.96 (m, 3H, (CH3)CH(CH3)O), 1.88 (br m, 6H, CH2), 2.14 (br m, 2H,
CH2),1.97–2.14 (m, 6H, p-CH3), 2.35 + 2.39 + 2.43 + 2.46 + 2.49 + 2.51
(6 Â s, 12H, o-CH3), 4.06 (m, 2H, NCH), 4.48 (m, 1H, CH(CH3)2), 6.64
(m, 1H, ArH), 6.97 (m, 1H, ArH), 7.09 (m, 1H, ArH), 7.25 (m, 4H,
Ar'H), 7.38 (m, 1H, ArH), 17.46 + 17.50 + 17.56 + 17.57 (4 Â bs, 1H,
solvent (CD2Cl2, 0.65 mL). The substrate (0.100 mmol) was added
and the mixture was heated to the given temperature. The progress
of the reaction was monitored by 1H NMR spectroscopy.
4.14. Diethyl 3-methylcyclopent-3-ene-1,1-dicarboxylate
Ru = CH) ppm. 19F NMR (282.23 MHz, CD2Cl2):
d
À81.7 (m, 6F,
3
CF3CF2CF2), À80.5–(À82.4) (m, 2F, CF3CF2CFF), À81.8–(À82.5) (m,
12F, CF3), À83.1–(À83.8) (m, 2F, CF3CF2CFF), À115.4 (m, 4F,
CF2CH2), À122.6 (m, 4F, CF2CF2CH2), À123.6 (m, 4F, CF2CF2CF2CH2),
À124.7 (m, 4F, CF3CF2CF2), À126.9 (m, 4F, CF3CF2CF2), À129.1 (m,
2F, CF), À130.7 (m, 4F, CF3CF2CF2) ppm. 13C NMR (75,44 MHz,
1H NMR (299.97 MHz, CDCl3) [29]:
d
1.22 (t, JH/H = 7.0 Hz, 6H,
CH2CH3),1.70 (s, 3H, CH3), 2.87 (m, 2H, CH2), 2.93 (m, 2H, CH2), 4.16
3
(q, JH/H = 7.0 Hz, 6H, CH2CH3), 5.18 (m, 1H, CH) ppm.
4.15. Diethyl 3,4-dimethylcyclopent-3-ene-1,1-dicarboxylate
CD2Cl2):
d
18.27 + 18.51 + 18.73
(3 Â s,
4C,
Ar'CH3-o),
20.02 + 20.16 + 20.60 (3 Â bs, 2C, OCH(CH3)), 21.29 + 21.39 (2 Â s,
1H NMR (299.97 MHz, toluene-d8) [30]:
6H, CH2CH3), 1.62 (s, 6H, CH3), 3.10 (s, 4H, CH2), 3.97 (q, JH/
H = 7.0 Hz, 6H, CH2CH3) ppm.
d
0.95 (t, 3JH/H = 7.3 Hz,
2
3
2C, p-CH3), 25.74 (m, 2C, CF2CH2CH2), 28.09 (t, JCÀF = 21.4 Hz, 2C,
CF2CH2CH2), 68.19 + 69.99 (2 Â s, 2C, CF2CH2CH2CH), 75.76 (m, 1C,
OCH(CH3)), 98.22–129.17 (m, 20C, CF3, CF2), 111.57 + 111.78 (2 Â s,
1C, CArH), 122.90 (s, 1C, CArH), 124.67 + 124.82 (2 Â s, 1C, CArH),
130.44 (2 Â s, 4C, CAr'H), 131.06 + 131.35 + 131.61 + 131.68 (4 Â s, 1C,
4.16. 2-(Prop-1-enyl)-2,5-dihydrofuran
3
CArH), 135.68 (bs, 2C, CAr'CH3), 137.63 + 137.78 + 138.79 + 138.98
1H NMR (299.97 MHz, CD2Cl2) [31]:
d
1.69 (dd, JHÀH = 5.7 Hz,
(4 Â s, 4C, CFCF3), 140.46 + 140.63 + 140.77 + 140.90 + 140.97 (5 Â s,
4C, CAr'CH3), 141.60 (s, 2C, CAr'N), 143.33 (m, 1C, CArCH = Ru), 154.14
(m, 1C, CArOiPr), 159.85 + 160.20 (2 Â s, 2C, COO), 214.49 + 214.79
(2 Â s, 1C, Ru = CNN), 320.75 (m, 1C, Ru = CH) ppm. MS (ESI), m/z (%)
1929 [M+Na]+ (100); 1577 [M-(C6F11O3)]+ (28); 1247 [M-(2 Â
C6F11O3)]+ (33); 999 (28). HRMS (ESI): calcd. for
4JH À H = 1.3 Hz, 3H, CHCH3), 4.59 (m, 2H, OCH2CHCH), 5.08–5.16
(bs, 1H, OCH), 5.43 (ddq, 3JH À H = 15.0 Hz, 3JH À H = 7.5 Hz,
4JH À H = 1.3 Hz, 1H, CH3CHCH), 5.64–5.76 (m, 2H, OCH2), 5.91
(dq, JH-H = 6.2 Hz, 4JH À H = 1.8 Hz, 1H, CH3CH) ppm.
3
4.17. Computational details
C
59H44F48N2NaO7Ru ([M+Na]+) 1929.1322, found 1929.1318.
DFT calculations were performed using Gaussian 09W program
suite [32] using the resolution-of-identity approach [33], recent
Minnesota MN12L pure functional [34], def2-SVP basis set [35] and
universal def2 auxiliary basis set [36]. Vibrational frequencies were
calculated for all species to characterize them as minima or
transition states. Vizualizations of the molecules were performed
with the GaussView program [37]. The geometries of all calculated
structures and their energies are listed in Supporting information
of this article.
4.12. [4,5-Bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-1,3-bis
(2,4,6-trimethylphenyl)-imidazolidin-2-ylidene](2-
isopropoxybenzylidene)bis[(2,4,4,5,5,6,6,6-octafluoro-3-oxahexan-
oyl)oxy)ruthenium(IV)(2b)
According to the general procedure, silver salt 3b (21 mg,
0.057 mmol) and complex 5 (HG2, 37 mg, 0.028 mmol) gave the
target complex 2b (44 mg, 88%, deep violet wax). 1H NMR
3
(399.94 MHz, CD2Cl2):
d
0.87 (d, JHÀH = 6.2 Hz, 3H, (CH3)CH
3
(CH3)O), 0.95 (d, JHÀH = 6.2 Hz, 3H, (CH3)CH(CH3)O), 1.75–1.97
(br m, 6H, CH2), 2.12–2.25 (br m, 2H, CH2), 2.20 + 2.21 (2 Â s, 6H, o-
CH3), 2.32 + 2.33 + 2.34 + 2.35 (4 Â s, 6H, o-CH3), 2.45 (s, 6H, p-CH3),
4.05 (m, 2H, NCH), 4.59 (m,1H, CH(CH3)2), 5.62 (dm, 2JH-F = 58.0 Hz,
2H, CHF), 6.67 (d, JHÀH = 7.9 Hz, 1H, ArH), 6.97 (tm, JHÀH = 7.5 Hz,
1H, ArH), 7.05 (m, 1H, ArH), 7.17 (m, 2H, Ar'H), 7.22 (m, 2H, Ar'H),
Acknowledgements
This work was supported by the Grant Agency of the Czech
Republic (No. 207/10/1533) and specific university research
(MSMT No. 20-SVV/2016). Computational resources were provided
by the MetaCentrum under the program LM2010005 and the
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