C. O'Beirne et al.
Inorganica Chimica Acta 486 (2019) 294–303
1
13
H
NMR (399.89 MHz, DMSO-d
6
,
ppm): 8.00–7.94 (2H, m,
C NMR (100.55 MHz, CDCl
3
, ppm): 171.1, 162.2, 134.0, 133.8,
CHAromatic), 7.15 (2H, t, J = 9.0 Hz, CHAromatic).
132.5, 132.2, 131.6, 131.5, 130.2, 130.1, 130.0, 128.8, 128.7, 123.2,
1
3
C NMR (100.55 MHz, DMSO-d
32.4, 132.3, 114.9, 144.7.
6
, ppm): 169.6, 165.1, 162.7, 133.9,
123.1, 116.0, 115.8.
1
31
9
1
F NMR (376.24 MHz, CDCl
3
3
, ppm): −113.83.
), ppm): 8.74.
1
9
F NMR (376.24 MHz, DMSO-d
6
, ppm): −111.99.
P NMR (282.11 MHz, CDCl
IR (ATR): 3068 (w, v), 1604 (m), 1499 (m), 1374 (s), 1229 (m),
155 (m), 852 (m), 771 (s), 688 (m), 619 (s), 503 (w), 410 (w).
Melting point: 220 °C.
IR (ATR): 3049 (w, v), 1591 (m), 1555 (m), 1478 (m), 1433 (m),
1371 (m), 1026 (m), 854 (m), 741 (s), 690 (s), 501 (s).
Melting Point: 140 °C.
1
Elemental Analysis calculated for C
.62; Found: C, 33.35; H, 1.44.
7
H
4
2
AgO F: Calculated: 34.04; H,
Elemental Analysis calculated for C43
4.44; Found: C, 66.60H, 5.33.
H
34
O
2
AgFP : C, 66.93; H,
2
1
2
2
.3. Synthesis of Triphenylphosphino-silver(I) benzoate complexes (5–8)
2.3.4. Bis-triphenylphosphino silver(I) 4-fluorobenzoate (8)
Triphenylphosphine (0.524 g, 2.00 mmol) and 4-fluoro-silver
benzoate (0.247 g, 1.00 mmol) were dissolved in 20 mL of dry di-
chloromethane. The mixture was stirred in the absence of light for 2 d
under nitrogen. The product was filtered in vacuo and washed with
20 mL of dry dichloromethane. The filtrate was concentrated to 2 mL
and 5 mL of pentane was added. The product was extracted and dried
.3.1. Bis-triphenylphosphino-silver(I) benzoate (5)
Triphenylphosphine (0.524 g, 2.00 mmol) and silver benzoate
(
0.229 g, 1.00 mmol) were dissolved in 20 mL of dry dichloromethane.
The mixture was stirred in the absence of light for 2 d under nitrogen.
The product was filtered in vacuo and washed with 20 mL of dry di-
chloromethane. The filtrate was concentrated to 2 mL and 5 mL of
pentane was added. The product was extracted and dried for 4 h in
for 4 h in vacuo to retrieve a light brown solid (0.650 g, 84% yield).
1
H NMR (399.89 MHz, CDCl , ppm): 8.11–8.02 (2H, m, CHAromatic),
3
vacuo to retrieve a white solid (0.596 g, 79% yield).
7.44–7.32 (19H, m, CHAromatic), 7.27 (6H, s, CHAromatic), 7.24 (5H, d,
1
H NMR (399.89 MHz, CDCl
3
, ppm): 8.14 (4H, dd, J = 8.3, 1.2 Hz,
J = 7 Hz, CHAromatic), 7.04–6.95 (2H, m, CHAromatic).
1
3
CHAromatic), 7.53–7.48 (10H, m, CHAromatic), 7.47 (10H, d, J = 3 Hz,
CHAromatic), 7.46–7.41 (8H, m, CHAromatic), 7.41–7.38 (3H, m,
CHAromatic).
C NMR (100.55 MHz, CDCl , ppm): 173.1, 164.9, 162.4, 133.0,
3
132.8, 131.3, 131.2, 131.1, 130.9, 130.3, 130.3, 130.0, 130.0, 129.0,
128.6, 128.4, 128.3, 127. 5, 127.4, 113.8, 113.6.
1
3
19
C NMR (100.55 MHz, CDCl
3
, ppm): 175.1, 134.6, 134.0, 133.8,
F NMR (376.24 MHz, CDCl , ppm): −112.72.
3
3
3
1
1
31.3, 131.2, 130.8, 130.0, 129.9, 129.5, 129.3, 129.2, 127.5.
P NMR (282.11 MHz, CDCl ), ppm): 8.56.
3
1
P NMR (282.11 MHz, CDCl
3
), ppm): 29.06.
IR (ATR): 3100 (w, v), 1606 (m), 1555 (m), 1478 (m), 1434 (m),
1370 (m), 1215 (m), 1146 (m), 1095 (m), 856 (m), 780 (7 8 0), 742 (s),
692 (s), 611 (s), 495 (s).
IR (ATR): 3100 (w), 2900 (w), 1592 (m), 1537 (m), 1434 (m), 1305
(
m), 1131 (w), 1095 (m), 691 (s), 489 (m).
Melting Point: 62 °C.
Melting Point: 152 °C.
Elemental Analysis calculated for C43
H
35AgO
P
2 2
: C, 68.53; H, 4.68;
Elemental Analysis calculated for C43
4.44; Found: C, 67.16; H, 4.70.
H
34
O
2
AgFP : C, 66.93; H,
2
A. Found: C, 68.25; H, 4.17.
2
.3.2. Triphenylphosphino silver(I) 2-fluorobenzoate (6)
2.4. Synthesis of 1,3-dibenzyl-4,5-diphenyl imidazol-2-ylidene silver(I)
Triphenylphosphine (0.262 g, 1.00 mmol) and 2-fluoro-silver
benzoate complexes (9–12)
benzoate (0.247 g, 1.00 mmol) were dissolved in 5 mL of dry di-
chloromethane. The mixture stirred in the absence of light for 2 d under
nitrogen. The product was filtered in vacuo and washed with 20 mL of
dry dichloromethane. The filtrate was concentrated to 2 mL and 5 mL of
pentane was added. The product was extracted and dried for 4 h in
1 mL of 1 M potassium tert-butoxide solution (1.00 mmol) was in-
jected at 0 °C to a mixture of 30 mL dry tetrahydrofuran and 1,3-di-
benzyl-4,5-diphenyl imidazolium bromide (0.481 g, 1.00 mmol), under
nitrogen. The reaction was stirred for 1 h at room temperature and al-
lowed to settle for 30 min. The solution was syringed from the reaction
flask and injected into a second flask containing 30 mL dry tetra-
hydrofuran and 1.00 mmol of the corresponding silver benzoate; all
additions are kept under nitrogen. The reaction mixture was stirred for
3 d under nitrogen. The reaction mixture was filtered in vacuo and re-
filtered using a grade 4 sinter funnel. The filtrate was removed under
reduced pressure to retrieve a solid that was dissolved in chloroform
and filtered using a grade 4 sinter funnel. The filtrate was filtered by
gravity filtration to remove remaining impurities and concentrated to
3 mL under reduced pressure. 80 mL of pentane was added and the
solution was allowed to sit for 24 h. The solid product was extracted
with pentane, filtered in vacuo and dried for 4 h.
vacuo to retrieve a light brown solid (0.342 g, 70% yield).
1
H NMR (399.89 MHz, CDCl , ppm): 7.85 (1H, td, J = 7.5, 2 Hz,
3
CHAromatic), 7.48–7.37 (10H, m, CHAromatic), 7.32 (7H, t, J = 7 Hz,
CHAromatic), 7.12–7.03 (1H, m, CHAromatic).
1
3
C NMR (100.55 MHz, CDCl , ppm): 171.5, 162.4, 159.9, 134.0,
3
1
33.8, 130.8, 130.7, 130.3, 128.9, 128.8, 123.2, 123.3, 116.3, 115.9.
1
3
9
1
F NMR (376.24 MHz, CDCl , ppm): −113.26.
3
P NMR (282.11 MHz, CDCl3), ppm): 11.22
IR (ATR): 3050 (w, v), 1591 (w), 1554 (w), 1476 (m), 1433 (m),
370 (m), 1093 (m), 854 (m), 795 (s), 691 (s), 654 (s), 542 (s), 503 (s).
Melting Point: 110 °C.
1
Elemental Analysis calculated for C25
H
19AgO FP: C, 58.96; H, 3.76;
2
Found: C, 58.78; H, 3.69.
2
.4.1. Synthesis of 1,3-dibenzyl-4,5-diphenyl imidazol-2-ylidene silver(I)
2.3.3. Bis-triphenylphosphino silver(I) 2-fluorobenzoate (7)
benzoate (9)
Triphenylphosphine (0.524 g, 2.00 mmol) and 2-fluoro-silver
20 mL of the carbene/THF solution is injected into a reaction flask
benzoate (0.247 g, 1.00 mmol) were dissolved in 30 mL of dry di-
chloromethane. The mixture was stirred in the absence of light for 2 d
under nitrogen. The product was filtered in vacuo and washed with
containing silver benzoate (0.228 g, 1.00 mmol) in 30 mL tetra-
hydrofuran at room temperature, whilst stirring. The reaction is stirred
for 3 d and worked up to achieve a brown solid (0.207 g, 33% yield).
1
2
0 mL of dry dichloromethane. The filtrate was concentrated to 2 mL
H
NMR (399.89 MHz, CDCl , ppm): 8.10 (2H, d, J = 8 Hz,
3
and 30 mL of pentane was added. The product was extracted and dried
CHAromatic), 7.44–7.34 (3H, m, CHAromatic), 7.28 (2H, t, J = 7.5 Hz,
CHAromatic), 7.24–7.19 (9H, m, CHAromatic), 7.03–6.96 (8H, m,
CHAromatic), 5.38 (4H, s, CH2Benzyl).
for 4 h in vacuo to retrieve a silver solid (0.713 g, 93% yield).
1
H NMR (399.89 MHz, CDCl , ppm): 7.77 (1H, td, J = 7.5, 2 Hz,
3
1
3
CHAromatic), 7.48–7.33 (16H, m, CHAromatic), 7.29 (15H, t, J = 7.5 Hz,
C NMR (100.55 MHz, CDCl , ppm): 179.7, 173.4, 136.1, 132.7,
3
CHAromatic), 7.10 – 7.00 (2H, m, CHAromatic).
130.6, 130.4, 129.5, 129.1, 128.6, 128.5, 127.9, 127.7, 127.3, 53.7.
296