ACS Catalysis
Research Article
ppm. Elemental analysis (%) calcd. for C26H21F18MoNO2: C,
38.21; H, 2.59; N, 1.71. Found: C, 38.03; H, 2.68; N, 1.86.
[Mo(N-2,6-Me2-C6H3)(IMes)(CHFc)(OTf)2] (6). [Mo(N-2,6-
Me2-C6H3)(IMes)(CHCMe2Ph)(OTf)2] (0.08 g, 8.00·10−2
mmol, 1 equiv) was dissolved in CH2Cl2 (4 mL), and vinyl
ferrocene (0.02 g, 8.00·10−2 mmol, 1 equiv), also dissolved in
CH2Cl2 (2 mL), was added to the mixture. After 1 day, the
solvent was removed, and the purple solid was repeatedly
washed with n-pentane, which yielded 6 (0.06 g, 5.68·10−2
mmol, 71% yield). 1H NMR (400 MHz, CDCl3): δ = 13.64 (s,
1JCH = 133 Hz, 1H, CH−Fc), 7.09 (s, 2H, Ar−H), 7.02 (s, 2H,
Ar−H), 6.99 (t, 3JHH = 7,7 Hz, 1H, Ar−H), 6.81 (d, 3JHH = 6,8
Hz, Ar−H), 6.72 (s, 2H, CHNC), 4.85 (s, 1H, Cp−H), 4.44 (s,
1H, Cp−H), 4.28 (s, 1H, Cp−H), 4.18 (s, 5H, Cpunsubst−H),
3.53 (s, 1H, Cp−H), 2.38 (s, 6H, CH3), 1.99 (s, 6H, CH3), 1.94
(s, 6H, CH3), 1.89 (s, 6H, CH3) ppm. 19F NMR (400 MHz,
CDCl3): δ = −75.15 (s, 3F, CF3SO2), −75.76 (s, 3F, CF3SO2)
ppm. 13C NMR (101 MHz, CDCl3): δ = 301.5 (s, CH−Fc),
184.3 (s, CNCarbene), 153.9 (s, Ar−C), 140.2 (s, Ar−C), 136.0 (s,
Ar−C), 135.0 (s, Ar−C), 134.7 (s, Ar−C), 130.0 (s, Ar−C),
129.7 (s, Ar−C), 128.9 (s, Ar−C), 127.3 (s, Ar−C), 119.5 (q,
CF3, 1JCF = 323.7 Hz), 93.8 (s, CC), 73.6 (s, Fe−C), 71.6 (s,
Fe−C), 70.3 (s, Fe−C), 69.6 (s, Fe−C), 66.3 (s, Fe−C), 21.0 (s,
CH3), 19.5 (s, CH3), 18.0 (s, CH3) ppm. Elemental analysis
calcd. (%) for C42H44F6FeMoN3O6S2: C, 49.62; H, 4.36; N,
4.13. Found: C, 49.89; H, 4.89; N, 3.85.
H)]−), 7.52 (s, 3H, Ar−H), 7.32 (s, 1H, Ar−H), 7.03 (d, 3JHH
=
7,65 Hz, 2H, Ar−H), 6.96 (s, 1H, Ar−H), 6.82 (s, 2H, CHNC),
4.76 (s, 1H, Cp−H), 4.68 (s, 1H, Cp−H), 4.51 (s, 1H, Cp−H),
4.14 (s, 6H, Cp−H, Cpunsubst−H), 2.35 (s, 6H, CH3), 2.07 (s,
6H, CH3), 1.86 (s, 6H, CH3), 1.84 (s, 6H, CH3) ppm. 19F NMR
(400 MHz, CDCl3): δ = −62.46 (s, 24F, Ar−CF3), −74.53 (s,
3F, CF3SO2) ppm. 13C NMR (101 MHz, CDCl3): δ = 297.8 (s,
1
Fc−CH), 182.1 (s, CNCarbene), 162.6−161.1 (q, JBC = 50 Hz,
B−Ar−C), 155.1 (s, Ar−C), 141.8 (s, Ar−C), 135.4 (s, Ar−C),
134.9 (s, Ar−C), 133.6 (s, Ar−C), 131.1 (s, Ar−C), 130.4 (s,
Ar−C), 130.0 (s, Ar−C), 129.5 (s, Ar−C), 129.2 (s, Ar−C),
128.9 (s, Ar−C), 128.5 (s, Ar−C), 126.0 (s, Ar−C), 125.9 (s,
Ar−C), 121.9 (q, CF3, 1JCF = 274.0 Hz), 117.6 (s, Ar−C), 91.1
(s, CCNHC), 75.7 (s, Fe−C), 73.4 (s, Fe−C), 73.0 (s, Fe−C),
70.3 (s, Fe−C), 67.7 (s, Fe−C), 21.1 (s, CH3), 19.3 (s, CH3),
17.4 (s, CH3) ppm. Elemental analysis calcd. (%) for
C74H55MoFeBO6S2N3F30: C, 50.05; H, 3.21; N, 2.43. Found:
C, 50.07; H, 3.39; N, 2.54.
[Mo(N-2,6-Me2-C6H3)(SIMes)(CHFc)(OTf)+ B(ArF)4 ] (9).
−
[Mo(N-2,6-Me2-C6H3)(SIMes)(CHFc)(OTf)2] (0.09 g, 8.41·
10−2 mmol, 1 equiv) was dissolved in CH2Cl2 (3 mL) under
stirring. Na[B(ArF)4] was dissolved in a mixture of CH2Cl2 and
diethyl ether (1:1, 2 mL) and added to the purple solution. After
one hour, the solvent was removed under reduced pressure. The
purple solid was dissolved in a minimum of CH2Cl2 and filtrated
through celite. By removing the solvent, 9 was obtained as a
purple solid (0.13 g, 7.48·10−2 mmol, 89% yield). 1H NMR (400
MHz, CD2Cl2): δ = 12.76 (s, 1H, CH−Fc), 7.74 (s, 9H, [B(Ar−
H)]−), 7.57 (s, 3H, [B(Ar−H)]−), 7.26 (t, 3JHH = 7.5 Hz, 1H,
Ar−H), 7.09 (m, 2H, Ar−H), 6.94 (s, 2H, Ar−H), 6.82 (s, 2H,
Ar−H), 4.77 (m, 1H, Cpsubst−H), 4.66 (m, 1H, Cpsubst−H), 4.53
(m, 1H, Cpsubst−H), 4.13 (m, 9H, CHCN + Cp−H), 3.29 (m,
1H, Cpsubst−H), 2.33 (s, 6H, CH3), 2.13 (m, 18H, CH3) ppm.
19F NMR (400 MHz, CD2Cl2): δ = −62.84 (s, 24F, Ar−CF3),
−74.22 (s, 3F, CF3SO2) ppm. 13C NMR (101 MHz, CD2Cl2): δ
= 300.0 (Fc−CH), 206.0 (CHCN), 163.1−162.6 (q, 1JBC = 50
Hz, B−Ar−C), 141.3 (Ar−C), 136.8 (Ar−C), 136.3 (Ar−C),
135.4 (Ar−C), 134.0 (Ar−C), 131.7 (Ar−C), 131.1 (Ar−C),
130.8 (Ar−C), 129.6 (Ar−C), 129.2 (Ar−C), 128.9 (Ar−C),
126.5 (Ar−C), 124.5 (q, CF3, 1JCF = 272.0 Hz), 118.0 (Ar−C),
91.6 (Fe−C), 76.2 (Fe−C), 73.9 (Fe−C), 73.6 (Fe−C), 70.6
(Fe−C), 68.6 (Fe−C), 21.3 (CH3), 19.8 (CH3), 18.1 (CH3)
ppm. Elemental analysis calcd. (%) for C73H57BF27FeMoN3O3S:
C, 50.63; H, 3.32; N, 2.43. Found: C, 50.36; H, 3.41; N, 2.36.
[Mo(N-2,6-Me2-C6H3)(SIMes)(CHFc)(OTf)2] (7). [Mo(N-2,6-
Me2-C6H3)(SIMes)(CHCMe2Ph)(OTf)2] (0.19 g, 1.96·10−1
mmol, 1 equiv) was dissolved in CH2Cl2 (3 mL), and vinyl
ferrocene (0.12 g, 5.89·10−1 mmol, 3 equiv), also dissolved in
CH2Cl2 (2 mL), was added to the mixture. After four hours, the
solvent was removed under reduced pressure. The purple solid
was repeatedly washed with n-pentane until the liquid phase no
longer took on a yellow-orange color. 7 was obtained as a purple
solid (0.17 g, 1.59·10−1 mmol, 81% yield). 1H NMR (400 MHz,
CDCl3): δ = 13.51 (s, 1JCH = 133 Hz, 1H, CH−Fc), 7.00 (t, 3JHH
= 7.6 Hz, 1H, Ar−H), 6.96 (s, 2H, Ar−H), 6.82 (d, 3JHH = 7.44
Hz, 2H, Ar−H), 6.69 (s, 2H, Ar−H), 4.79 (s, 1H, Cp−H), 4.42
(s, 1H, Cp−H), 4.26 (s, 1H, Cp−H), 4.15 (s, 5H, Cpunsusbt−H),
3.92 (m, 4H, CH2NC), 3.45 (s, 1H, Cp−H), 2.33 (s, 6H, CH3),
2.22 (s, 6H, CH3), 2.15 (s, 6H, CH3), 1.94 (s, 6H, CH3) ppm.
19F NMR (400 MHz, CDCl3): δ = −74.87 (s, 3F, CF3SO2),
−75.82 (s, 3F, CF3SO2) ppm. 13C NMR (101 MHz, CDCl3): δ
= 302.6 (s, CH−Fc), 208.4 (s, CNCarbene), 153.9 (s, Ar−C),
139.5 (s, Ar−C), 136.8 (s, Ar−C), 135.8 (s, Ar−C), 134.8 (s,
Ar−C), 130.4 (s, Ar−C), 130.1 (s, Ar−C), 129.1 (s, Ar−C),
127.4 (s, Ar−C), 119.6 (q, CF3, 1JCF = 318.1 Hz), 94.0 (s, C
ASSOCIATED CONTENT
■
sı
* Supporting Information
CNHC), 73.7 (s, Fe−C), 71.8 (s, Fe−C), 70.5 (s, Fe−C), 69.8 (s,
The Supporting Information is available free of charge at
Fe−C), 66.4 (s, Fe−C), 52.3 (s, CH3), 21.2 (s, CH3), 19.7 (s,
CH3), 18.4 (s, CH3), 18.3 (s, CH3) ppm. Elemental analysis (%)
calcd. for C42H46F6FeMoN3O6S2: C, 49.52; H, 4.55; N, 4.12.
Found: C, 49.11; H, 4.90; N, 4.06.
Crystallographic information for 1 (CIF)
Crystallographic information for 2 (CIF)
Crystallographic information for 3 (CIF)
Crystallographic information for 4 (CIF)
Crystallographic information for 5 (CIF)
Crystallographic information for 6 (CIF)
[Mo(N-2,6-Me2-C6H3)(IMes)(CHFc)(OTf)+ B(ArF)4 ] (8).
−
[Mo(N-2,6-Me2-C6H3)(IMes)(CHFc)(OTf)2] (0.08 g, 7.88·
10−2 mmol, 1 equiv) was dissolved in CH2Cl2 (3 mL) under
stirring. Na[B(ArF)4] (0.09 g, 7.88·10−2 mmol, 1 equiv) was
dissolved in a mixture of CH2Cl2 and diethyl ether (1:1, 2 mL)
and added to the purple solution. After one hour, the solvent was
removed under reduced pressure. The purple solid was dissolved
in a minimum of CH2Cl2 and filtrated through celite. By
removing the solvent, 8 was obtained as a purple solid (0.124 g,
7.26·10−2 mmol, 92% yield). 1H NMR (400 MHz, CDCl3): δ =
Additional characterizations and compound synthesis,
experimental procedures, analysis, and full character-
ization; NMR spectra; force field and simulation
parameters and analysis of simulated data (PDF)
1
12.87 (s, JCH = 127 Hz, 1H, CH−Fc), 7.72 (s, 12H, [B(Ar−
14820
ACS Catal. 2020, 10, 14810−14823