Organometallics
Article
This complex was prepared following the synthetic procedure
described for 20a starting from 500 mg of 9b (1.17 mmol). 20b
was collected as a brownish white solid (410 mg, 0.768 mmol, 65.6%).
Mp: 200−225 °C. 1H NMR (500 MHz, CDCl3): δ 7.48−7.35 (m, Ar-
H, 5 H), 7.34 (t, J = 7.7 Hz, Ar-H, 1 H), 7.21 (dd, J = 7.7, 1.2 Hz, Ar-
H, 1 H), 7.14 (dd, J = 7.7, 1.2 Hz, Ar-H, 1 H), 5.60 (q, J = 7.1 Hz,
CH, 1 H), 3.91 (dd, J = 11.8, 10.2 Hz, CH, 1 H), 3.50/3.34 (m+t, J =
11.8 Hz, CH2, 2 H), 3.47 (sp, J = 6.8 Hz, CH, 1 H), 2.64 (sp, J = 6.9
Hz, CH, 1 H), 1.74 (d, J = 7.1 Hz, CH3, 3 H), 1.50 (d, J = 6.8 Hz,
CH3, 3 H), 1.32 (d, J = 6.8 Hz, CH3, 3 H), 1.26 (d, J = 6.9 Hz, CH3, 3
H), 1.22 (d, J = 6.9 Hz, CH3, 3 H), 0.77 (s, CH3, 9 H). 13C NMR
(125 MHz, CDCl3): δ 208.1, 146.6, 146.0, 138.3, 137.2, 129.5, 129.1,
128.6, 127.0, 125.6, 125.2, 76.1, 59.3, 46.1, 29.1, 28.2, 27.8, 26.5, 26.2,
23.7, 23.5, 17.1. HRMS: calcd for C27H38AgClN2 [M]+ 532.1774,
found 532.1769.
collected as a white solid (804 mg, 1.57 mmol, 79.6%). Mp: 185−187
°C. 1H NMR (500 MHz, CDCl3): δ 7.32 (t, J = 7.8 Hz, Ar-H, 1 H),
7.18 (dd, J = 7.8, 1.3 Hz, Ar-H, 1 H), 7.13 (dd, J = 7.8, 1.3 Hz, Ar-H,
1 H), 4.18 (q, J = 7.0 Hz, CH, 1 H), 4.02 (t, J = 11.3 Hz, CH, 1 H),
3.79/3.61 (t+t, J = 11.3 Hz, J = 11.3 Hz, CH2, 2 H), 3.40 (sp, J = 6.9
Hz, CH, 1 H), 2.78 (sp, J = 6.8 Hz, CH, 1 H), 1.45 (d, J = 6.9 Hz,
CH3, 3 H), 1.34 (d, J = 7.0 Hz, CH3, 3 H), 1.32 (d, J = 6.9 Hz, CH3, 3
H), 1.29 (d, J = 6.8 Hz, CH3, 3 H), 1.16 (d, J = 6.8 Hz, CH3, 3 H),
1.07 (s, CH3, 9 H), 0.79 (s, CH3, 9 H). 13C NMR (125 MHz,
CDCl3): δ 201.5, 146.6, 146.4, 137.0, 129.4, 125.5, 125.2, 75.8, 66.0,
48.1, 35.2, 34.7, 29.0, 28.1, 28.0, 27.7, 26.7, 26.2, 23.7, 23.5, 13.7.
HRMS: calcd for C25H42AgClN2 [M]+ 512.2087, found 512.2082.
[(4S)-4-tert-Butyl-3-(2,6-diisopropylphenyl)-1-(2-
isopropylphenyl)imidazolidin-2-ylidene]silver(I) Chloride
(20g). This complex was prepared following the synthetic procedure
described for 20a starting from 500 mg of 9g (1.14 mmol). 20g was
collected as a white solid (374 mg, 0.683 mmol, 60.2%). Mp: 200−
[(4S)-4-tert-Butyl-3-(2,6-diisopropylphenyl)-1-[(1S)-1-(1-
naphthyl)ethyl]imidazolidin-2-ylidene]silver(I) Chloride (20c).
This complex was prepared following the synthetic procedure
described for 20a starting from 1.50 g of 9c (3.14 mmol). 20c was
collected as an off-white solid (1.37 g, 2.34 mmol, 74.5%). Mp: 199−
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209 °C. H NMR (500 MHz, CDCl3): δ 7.46−7.20 (m, Ar-H, 4 H),
7.36 (t, J = 7.7 Hz, Ar-H, 1 H), 7.22 (dd, J = 7.7, 1.5 Hz, Ar-H, 1 H),
7.18 (dd, J = 7.7, 1.5 Hz, Ar-H, 1 H), 4.25 (br m, CH, 1 H), 4.13/
3.92 (br m+t, J = 11.2 Hz, CH2, 2 H), 3.51 (sp, J = 6.8 Hz, CH, 1 H),
3.18 (br m, CH, 1 H), 2.93 (sp, J = 6.8 Hz, CH, 1 H), 1.46 (d, J = 6.8
Hz, CH3, 3 H), 1.42 (d, J = 6.8 Hz, CH3, 3 H), 1.36 (d, J = 6.8 Hz,
CH3, 3 H), 1.33 (br d, J = 6.8 Hz, CH3, 6 H), 1.24 (d, J = 6.8 Hz,
CH3, 3 H), 0.88 (s, CH3, 9 H). 13C NMR (125 MHz, CDCl3): δ
208.0, 146.5, 145.9, 138.0, 130.0, 129.6, 128.0, 127.6, 125.6, 125.3,
56.3, 29.4, 28.4, 26.7, 26.2, 23.8, 23.6. HRMS: calcd for
C28H40AgClN2 [M]+ 546.1931, found 546.1955.
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201 °C. H NMR (500 MHz, CDCl3): δ 8.32−7.49 (m, Ar-H, 7 H),
7.35 (t, J = 6.8 Hz, Ar-H, 1 H), 7.21 (dd, J = 7.7, 1.0 Hz, Ar-H, 1 H),
7.15 (dd, J = 7.7, 1.0 Hz, Ar-H, 1 H), 6.16 (q, J = 6.8 Hz, CH, 1 H),
3.96 (dd, J = 11.9, 10.4 Hz, CH, 1 H), 3.66/2.71 (t+t, J = 11.9 Hz, J =
10.4 Hz, CH2, 2 H), 3.46 (sp, J = 6.7 Hz, CH, 1 H), 2.75 (sp, J = 6.9
Hz, CH, 1 H), 1.96 (d, J = 6.9 Hz, CH3, 3 H), 1.61 (d, J = 6.9 Hz,
CH3, 3 H), 1.34 (d, J = 7.0 Hz, CH3, 3 H), 1.27 (d, J = 6.9 Hz, CH3, 3
H), 1.20 (d, J = 6.7 Hz, CH3, 3 H), 0.40 (s, CH3, 9 H). 13C NMR
(125 MHz, CDCl3): δ 208.2, 146.5, 146.1, 137.0, 134.1, 133.2, 131.4,
129.9, 129.5, 129.3, 126.8, 126.4, 125.5, 125.2, 124.6, 123.6, 75.4,
56.0, 47.1, 29.1, 28.1, 27.7, 26.3, 26.2, 23.7, 23.6, 18.6. HRMS: calcd
for C31H40AgClN2 [M]+ 582.1931, found 582.1925.
[(4S)-4-tert-Butyl-1-(2-tert-butylphenyl)-3-(2,6-
diisopropylphenyl)imidazolidin-2-ylidene]silver(I) Chloride
(20h). This complex was prepared following the synthetic procedure
described for 20a starting from 200 mg of 9h (0.440 mmol). 20h was
collected as a yellow solid (215 mg, 0.383 mmol, 87.1%). Mp: 122−
[(4S)-4-tert-Butyl-3-(2,6-diisopropylphenyl)-1-[(1R)-1-(1-
naphthyl)ethyl]imidazolidin-2-ylidene]silver(I) Chloride (20d).
This complex was prepared following the synthetic procedure
described for 20a starting from 1.00 g of 9d (2.10 mmol). 20d was
collected as an off-white solid (1.01 mg, 1.73 mmol, 82.7%). Mp:
230−252 °C. 1H NMR (500 MHz, CDCl3): δ 8.29−7.50 (m, Ar-H, 7
H), 7.36 (t, J = 7.7 Hz, Ar-H, 1 H), 7.23 (dd, J = 7.7, 1.1 Hz, Ar-H, 1
H), 7.15 (dd, J = 7.7, 1.0 Hz, Ar-H, 1 H), 6.19 (q, J = 6.8 Hz, CH, 1
H), 3.78 (t, J = 11.2 Hz, CH, 1 H), 3.48 (sp, J = 6.8 Hz, CH, 1 H),
3.40/2.87 (t+t, J = 11.2 Hz, J = 11.2 Hz, CH2, 2 H), 2.59 (sp, J = 6.8
Hz, CH, 1 H), 1.94 (d, J = 6.9 Hz, CH3, 3 H), 1.55 (d, J = 6.8 Hz,
CH3, 3 H), 1.34 (d, J = 6.8 Hz, CH3, 3 H), 1.27 (d, J = 6.7 Hz, CH3, 3
H), 1.15 (d, J = 6.8 Hz, CH3, 3 H), 0.72 (s, CH3, 9 H). 13C NMR
(125 MHz, CDCl3): δ 210.2, 146.6, 146.1, 137.1, 134.1, 132.8, 131.8,
129.9, 129.5, 129.2, 127.3, 126.5, 125.5, 125.3, 125.2, 124.8, 123.4,
76.0, 56.0, 46.5, 28.8, 28.2, 27.8, 26.5, 26.4, 23.7, 23.6, 19.0. HRMS:
calcd for C31H40AgClN2 [M]+ 582.1931 found 582.1925.
[(4S)-4-tert-Butyl-3-(2,6-diisopropylphenyl)-1-[(1S)-1,2,2-
trimethylpropyl]imidazolidin-2-ylidene]silver(I) Chloride
(20e). This complex was prepared following the synthetic procedure
described for 20a starting from 900 mg of 9e (2.21 mmol). 20e was
collected as a brownish white solid (677 mg, 1.32 mmol, 59.6%). Mp:
198−216 °C. 1H NMR (500 MHz, CDCl3): δ 7.32 (t, J = 7.7 Hz, Ar-
H, 1 H), 7.18 (dd, J = 7.7, 1.3 Hz, Ar-H, 1 H), 7.13 (dd, J = 7.7, 1.3
Hz, Ar-H, 1 H), 4.15 (q, J = 7.0 Hz, CH, 1 H), 4.07 (dd, J = 11.9, 10.7
Hz, CH, 1 H), 3.88/3.63 (t+t, J = 11.9 Hz, J = 10.7 Hz, CH2, 2 H),
3.41 (sp, J = 6.7 Hz, CH, 1 H), 2.69 (sp, J = 6.8 Hz, CH, 1 H), 1.43
(d, J = 6.7 Hz, CH3, 3 H), 1.34 (d, J = 7.0 Hz, CH3, 3 H), 1.33 (d, J =
6.8 Hz, CH3, 3 H), 1.30 (d, J = 6.7 Hz, CH3, 3 H), 1.18 (d, J = 6.8 Hz,
CH3, 3 H), 1.06 (s, CH3, 9 H), 0.81 (s, CH3, 9 H). 13C NMR (125
MHz, CDCl3): δ 201.5, 146.8, 146.0, 137.2, 129.4, 125.4, 125.3, 76.3,
66.2, 48.5, 35.5, 34.9, 29.1, 28.2, 28.0, 27.4, 26.8, 26.2, 23.8, 23.5,
14.0. HRMS: calcd for C25H42AgClN2 [M]+ 512.2087, found
512.2082.
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124 °C. H NMR (500 MHz, CDCl3): δ 7.60−7.01 (m, Ar-H, 4 H),
7.37/7.36 (t, J = 7.7 Hz, Ar-H, 1 H), 7.23/7.21 (dd, J = 7.7, 1.5 Hz,
Ar-H, 1 H), 7.19/7.18 (dd, J = 7.7, 1.5 Hz, Ar-H, 1 H), 7.08/7.06 (dd,
J = 7.7, 1.5 Hz, Ar-H, 1 H), 4.44−3.69 (m, CH, CH2, 3 H), 3.51/3.49
(sp, J = 6.8 Hz, CH, 1 H), 2.98/2.94 (sp, J = 6.8 Hz, CH, 1 H), 1.53/
1.53 (s, CH3, 9 H), 1.46/1.43 (d, J = 6.8 Hz, CH3, 3 H), 1.40/1.40 (d,
J = 6.8 Hz, CH3, 3 H), 1.36/1.34 (d, J = 6.8 Hz, CH3, 3 H), 1.20/1.20
(d, J = 6.8 Hz, CH3, 3 H), 0.87/0.85 (s, CH3, 9 H). 13C NMR (125
MHz, CDCl3): δ 214.6, 147.0, 146.6, 146.4, 145.9, 145.6, 140.0,
131.5, 131.2, 129.7, 129.6, 129.6, 129.5, 129.3, 128.3, 128.2, 125.6,
125.3, 125.4, 125.3, 76.4, 76.3, 58.1, 58.0, 34.4, 34.3, 32.9, 32.6, 29.8,
29.5, 29.3, 28.4, 27.6, 27.2, 27.0, 26.4, 26.3, 23.9, 23.7, 23.7, 23.3.
HRMS: calcd for C29H42AgClN2 [M]+ 560.2087, found 560.2247.
[(4S)-4-tert-Butyl-3-(2-tert-butylphenyl)-1-[(1S)-1-
phenylethyl]imidazolidin-2-ylidene]silver(I) Chloride (20i).
This complex was prepared following the synthetic procedure
described for 20a starting from 60 mg of 9i (0.150 mmol). 20i was
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collected as a yellowish white solid (64 mg, 0.127 mmol, 84.1%). H
NMR (500 MHz, CDCl3): δ 7.50 (dd, J = 7.9, 1.5 Hz, Ar-H, 1 H),
7.45−7.33 (m, Ar-H, 5 H), 7.37 (dd, J = 7.9, 1.5 Hz, Ar-H, 1 H), 7.30
(td, J = 7.9, 1.5 Hz, Ar-H, 1 H), 7.21 (td, J = 7.9, 1.5 Hz, Ar-H, 1 H),
5.51 (q, J = 7.1 Hz, CH, 1 H), 4.25 (dd, J = 11.9, 6.0 Hz, CH, 1 H),
3.75/3.15 (t+dd, J = 11.9 Hz, J = 11.9, 6.0 Hz, CH2, 2 H), 1.70 (d, J =
7.1 Hz, CH3, 3 H), 1.43 (s, CH3, 9 H), 0.54 (s, CH3, 9 H). 13C NMR
(125 MHz, CDCl3): δ 204.9, 146.1, 140.0, 138.2, 133.0, 130.2, 129.0,
128.9, 128.6, 127.3, 127.3, 74.3, 74.3, 59.3, 46.7, 46.6, 36.4, 35.6, 32.5,
26, 17.3. HRMS: calcd for C25H34AgClN2 [M]+ 504.1461 found
504.1472.
[(4R)-1-[(1S)-1-(1-Adamantyl)ethyl]-4-tert-butyl-3-(2,6-
diisopropylphenyl)imidazolidin-2-ylidene]silver(I) Chloride
(21a). This complex was prepared following the synthetic procedure
described for 20a starting from 216 mg of 14a (0.445 mmol). 21a was
collected as a pinkish solid (99 mg, 0.167 mmol, 37.6%). Mp: 223−
234 °C. 1H NMR (500 MHz, CDCl3): δ 7.32 (t, J = 7.8 Hz, Ar-H, 1
H), 7.18 (dd, J = 7.8, 1.6 Hz, Ar-H, 1 H), 7.12 (dd, J = 7.8, 1.6 Hz,
Ar-H, 1 H), 4.02 (t, J = 11.4 Hz, CH, 1 H), 3.98 (br., CH, 1 H), 3.78/
3.61 (t+t, J = 11.4 Hz, J = 11.4 Hz, CH2, 2 H), 3.42 (sp, J = 6.8 Hz,
[(4S)-4-tert-Butyl-3-(2,6-diisopropylphenyl)-1-[(1R)-1,2,2-
trimethylpropyl]imidazolidin-2-ylidene]silver(I) Chloride
(20f). This complex was prepared following the synthetic procedure
described for 20a starting from 800 mg of 9f (1.97 mmol). 20f was
N
Organometallics XXXX, XXX, XXX−XXX