196
Z. Lamprecht et al. / Polyhedron 158 (2019) 193–207
(C2), 123.1 (C3), 125.1 (C4), 127.2 (C5), 155.2 (C20), 143.7 (C30),
131.4 (C40), 134.6 (C50), 78.1 (CH2), 14.1 (CH3).
[MꢁCO]ꢁ), 635.0027 (100%, [M+H-2CO]ꢁ), 578.0072 (32%,
[Mꢁ4CO]ꢁ).
4a: Yield: 0.12 g (0.2 mmol, 11%), red crystals.
m
CO(hexane)/
In an effort to obtain pure triscarbene complex 18a and to
improve the yield, a 1:3 ratio of reagents (2,30-bithiophene:n-
BuLi/M(CO)6) was also used, however without significant effect.
2.4.1.1.3. Synthesis of 3,30-bithienyl chromium carbene complexes.
0.34 g (2.0 mmol) of 3,30-bithiophene was dissolved in 15 mL
THF, 1.90 mL (3.0 mmol) of n-BuLi and 0.67 g (3.0 mmol) Cr(CO)6
were added. 0.8 g (4.0 mmol) [Et3O][BF4], dissolved in 10 mL
DCM, was added to the reaction mixture dissolved in DCM. Five
complexes were isolated. Compound 2b was first to elute from
the column, followed in order by 1b, 11b, 10b and 16b.
cmꢁ1 2066 m (A1(1)), 1983sh (B), 1943 s (E). d1H(400 MHz; CDCl3;
3
3
3
Me4Si) 7.26 (1H, J5,3 1.1, J4,3 3.7, dd, H3), 7.08 (1H, dd, J4,3 3.7,
3
3
3J4,5 5.1, H4), 7.28 (1H, dd, J5,3 1.1, J5,4 5.1, H5), 7.82 (1H, d,
J4 ,2 1.4, H20), 8.25 (1H, d, J2 ,4 1.4, H40), 5.01 (2H, q, 3J 7.1, CH2),
4
4
0
0
0
0
1.68 (3H, t, 3J 7.1, CH3). d13C(100.613 MHz; CDCl3; Me4Si) 290.7
(Ccarb), 202.4 (COtrans), 197.5 (COcis), 137.6 (C2), 124.0 (C3), 125.0
(C4), 128.0 (C5), 129.6 (C20), 138.2 (C30), 137.2 (C40), 158.6 (C50),
78.7 (CH2), 15.0 (CH3). m/z(C16H10O6S2W, 545.9428 g/mol),
545.9514 (27%, [M]ꢁ), 517.9565 (28%, [MꢁCO]ꢁ), 489.9644 (37%,
[Mꢁ2CO]ꢁ), 461.9698 (26%, [Mꢁ3CO]ꢁ), 433.9734 (100%,
[Mꢁ4CO]ꢁ), 405.9771 (8%, [Mꢁ5CO]ꢁ).
1b: Yield: 0.26 g (0.63 mmol, 31%), red crystals. mCO(hexane)/
cmꢁ1 2059 m (A(11)), 1987vw (B1), 1958sh (A(12)), 1947vs (E). d1H
3
5a: Yield: 0.07 g (0.1 mmol, 6%), orange-brown crystals.
(300.13 MHz; CDCl3; Me4Si) 7.07 (1H, d, J4,5 4.0, H4), 7.62 (1H,
3
m
CO(hexane)/cmꢁ1 2065 m (A1(1)), 1955sh(A(12)), 1946 s (E). d1H
d, J5,4 4.0, H5), 7.13 (1H, s, H20), 6.94 (1H, s, H40), 7.33 (1H, s,
3
(400 MHz; CDCl3; Me4Si) 7.33 (1H, d, J3,4 5.3, H3), 7.73 (1H, d,
H50), 4.73 (2H, q, 3J 6.5, CH2), 1.20 (3H, t, 3J 6.5, CH3). d13C
(75.468 MHz; CDCl3; Me4Si) 330.1 (Ccarb), 223.5 (COtrans), 216.3
(COcis), 153.0 (C2), 137.2 (C3), 130.1 (C4), 132.1 (C5), 122.4 (C20),
130.7 (C30), 128.1 (C40), 125.7 (C50), 76.4 (CH2), 14.3 (CH3).
3
4
4
J4,3 5.3, H4), 7.39 (1H, dd, J2 ,4 1.1, J2 ,5 3.6, H20), 7.35 (1H, dd,
0
0
0
0
4
3
4
3
J4 ,2 1.1, J4 ,5 5.1, H40), 7.57 (1H, dd, J5 ,2 3.6, J5 ,4 5.1, H50),
0
0
0
0
0
0
0
0
5.07 (2H, q, 3J 7.1, CH2), 1.67 (3H, t, 3J 7.1, CH3).
d
13C
(100.613 MHz; CDCl3; Me4Si) 288.4(Ccarb), 202.4 (COtrans), 147.1
(C5), 128.7 (C3), 141.5 (C4), 132.2 (C20), 132.7 (C40), 133.3 (C50),
77.9 (CH2), 15.1 (CH3).
2b: Yield: 0.20 g (0.48 mmol, 24%), red crystals. mCO(hexane)/
cmꢁ1 2059 m (A(11)), 1983vw (B1), 1958sh (A(12)), 1947vs (E). d1H
(300.13 MHz; CDCl3; Me4Si) 7.71 (1H, s, H2), 8.40 (1H, s, H4),
4
3
7.47 (1H, d, J2 ,5 3.2, H20), 7.34 (1H, d, J4 ,5 5.2, H40), 7.41 (1H,
0
0
0
0
14a: Yield: 0.52 g (0.6 mmol, 28%), brown red crystals.
3
4
CO(hexane)/cmꢁ1 2064 m (A1(1)), 1984vw (B1), 1955sh (A(12)),
dd, J5 ,4 5.2 and J5 ,2 3.2, H50), 5.20 (2H, q, 3J 7.1, CH2), 1.69 (3H,
t, 3J 7.1, CH3). d13C(100.613 MHz; CDCl3; Me4Si) 316.3 (Ccarb),
223.2 (COtrans), 217.1 (COcis), 129.1 (C2), 139.0 (C3), 138.9 (C4),
155.4 (C5), 120.8 (C20), 136.0 (C30), 126.0 (C40), 126.8 (C50), 76.1
(CH2), 15.2 (CH3)
0
0
0
0
m
3
1944vs (E). d1H(400 MHz; CDCl3; Me4Si) 7.38 (1H, d, J3,4 4.3,
3
4
H3), 8.15 (1H, d, J4,3 4.3, H4), 8.02 (1H, d, J2 ,4 1.3, H20), 8.26
0
0
(1H, d, J4 ,2 1.3, H40), 5.01 (2H, q, 3J 7.0, CH2), 5.03 (2H, q, 3J
7.0, CH2), 1.69 (3H, t, 3J 7.0, CH3), 1.68 (3H, t, 3J 7.0, CH3). d13C
(100.613 MHz; CDCl3; Me4Si) 291.1(C-50)(Ccarb), 288.1(C-5)(Ccarb),
202.5 and 202.2 (COtrans), 197.6 and 197.3 (COcis), 147.3 (C2),
125.6 (C3), 143.4 (C30), 156.3 (C5), 136.1 (C20), 131.6 (C4),
137.0 (C40), 159.5 (C50), 78.9 and 78.4 (CH2), 15.0 and 14.9
(CH3). m/z(C24H14O12S2W2, 925.8946 g/mol), 925.9067 (51%,
[M]ꢁ), 897.9121 (100%, [MꢁCO]ꢁ), 869.9167 (28%, [Mꢁ2CO]ꢁ),
841.9157 (7%, [Mꢁ3CO]ꢁ), 813.9256 (13%, [Mꢁ4CO]ꢁ),
785.9268 (11%, [Mꢁ5CO]ꢁ).
4
0
0
10b: Yield: 0.40 g (0.60 mmol, 30%), purple-red crystals.
m
CO(hexane)/cmꢁ1 2059 m (A1(1)), 1984vw (B1), 1959sh (A(12)),
1948vs (E). d1H(300.13 MHz; CDCl3; Me4Si): 7.77 (2H, s, H2), 8.39
(2H, s, H4), 5.22 (4H, q, 3J 6.7, CH2), 1.70 (6H, t, 3J 6.9, CH3). d13C
(75.468 MHz; CDCl3; Me4Si) 316.9 (Ccarb), 223.1 (COtrans), 217.0
(COcis), 129.4 (C2), 137.6 (C3), 138.3 (C4), 155.8 (C5), 76.2 (CH2),
15.2 (CH3). m/z(C24H14O12S2Cr2, 661.87 g/mol) 576.8508 (50%,
[MꢁHꢁ3CO]ꢁ), 548.8428 (100%, [MꢁHꢁ4CO]ꢁ), 520.8489 (94%,
[MꢁHꢁ5CO]ꢁ).
15a: Yield: 0.17 g (0.2 mmol, 9%), dark brown crystals. d1H
3
(400 MHz; CDCl3; Me4Si) 7.03 (1H, dd, J4,3 3.8, H3) 7.05 (1H, dd,
11b: Yield: <3%, purple-red crystals. d1H(300.13 MHz; CDCl3;
3J4,3 3.6, J4,5 5.0, H4), 7.34 (1H, d, J4,5 5.0, H5), 7.98 (1H, s, H40),
Me4Si) 7.47 (2H, d, J4,5 4.4, H4), 8.18 (2H, d, J5,4 4.4, H5), 5.18
3
3
3
3
4.79 (2H, q, 3J 6.5, CH2), 1.38 (3H, t, 3J 7.1, CH3).
d
13C
(4H, q, 3J 7.0, CH2), 1.70 (6H, t, 3J 7.0, CH3).
(100.613 MHz; CDCl3; Me4Si) 290.9 (C-50)(Ccarb), 305.8 (C-20)(Ccarb),
203.4 (COtrans), 197.1 and 196.4 (COcis), 128.3 (C2), 126.8 (C3),
126.4 (C4), 127.4 (C5), 157.7 (C20), 136.4 (C30), 139.5 (C40), 158.0
(C50), 79.4 and 78.8 (CH2), 14.9 and 14.2 (CH3).
2.4.1.1.4. Synthesis of 2,30-bithienyl chromium carbene complexes.
0.33 g (2.0 mmol) of 2,30-bithiophene was dissolved in 10 mL
THF, 1.9 mL (3.0 mmol) of n-BuLi and 0.66 g (3.0 mmol) of Cr
(CO)6 were added. Dissolved in 20.00 mL DCM, the reaction was
alkylated with 0.57 g (3.0 mmol) [Et3O][BF4]. Compounds 4b, 3b
and 5b eluted first, followed by the biscarbene complexes 14b
and 16b.
16a: Yield: 0.21 g (0.2 mmol, 11%), blue crystals. mCO(hexane)/
cmꢁ1 2064 m (A(11)), 1992vw (B1), 1955 m (A(12)), 1946vs (E). d1H
3
(400 MHz; CDCl3; Me4Si) 8.09 (2H, d, J3,4 4.3, H3/H30), 7.48 (2H,
3
d, J4,3 4.3, H4/H40), 5.00 (2H, q, 3J 7.1, CH2), 1.68 (3H, t, 3J 7.1,
3b: Yield: 0.10 g (0.2 mmol, 12%), red crystals. d1H(300 MHz;
3
CH3).
d
13C(100.613 MHz; CDCl3; Me4Si) 288.5 (Ccarb), 202.4
CDCl3; Me4Si) 7.08 (1H, dd, H3), 7.36 (1H, dd, J4,5 4.1, H4), 7.39
3
3
(1H, dd, J5,4 4.1, H5), 7.63 (1H, br, H40), 8.22 (1H, J5 ,4 4.3, H50),
0
0
(COtrans), 197.4 (COcis), 145.4 (C2), 127.0 (C3), 145.4 (C4), 157.8
(C5),
78.5
(CH2),
15.0
(CH3).
m/z(C24H14O12S2W2),
5.17 (2H, q, 3J 7.0, CH2), 1.67 (3H, t, 3J 7.0, CH3). 13C
d
925.8946 g/mol, 925.8946 (61%, [M]ꢁ), 897.9146 (100%, [MꢁCO]ꢁ),
869.9189 (39%, [Mꢁ2CO]ꢁ), 841.9185 (15%, [Mꢁ3CO]ꢁ), 813.9267
(12%, [Mꢁ4CO]ꢁ), 785.9278 (14%, [Mꢁ5CO]ꢁ).
(100.613 MHz; CDCl3; Me4Si) 312.4 (Ccarb), 223.4 (COtrans), 217.2
(COcis). 148.5 (C2), 123.1 (C3), 125.2 (C4), 127.2 (C5), 155.3 (C20),
142.9 (C30), 129.2 (C40), 134.5 (C50), 75.7 (CH2), 15.1 (CH3).
19a: Yield: 0.08 g (0.1 mmol, 5%), reddish brown crystals.
4b: Yield: 0.12 g (0.3 mmol, 15%), red crystals.
mCO(hexane)/
m
CO(hexane)/cmꢁ1 2066 m (A1(1)), 1980vw (B1), 1943 s (E). d1H
cmꢁ1 2059 m (A(11)), 1984vw (B), 1959sh (A(12)), 1948 s (E). d1H
3
4
3
(500 MHz; CDCl3; Me4Si) 7.61 (1H, d, J3,4 4.3, H3), 8.11 (1H, d,
3J4,3 4.3, H4), 7.88 (1H, s, H40), 4.99 (2H, q, 3J 7.1, CH2), 1.66 (3H,
t, 3J 7.1, CH3), 4.40 (2H, q, 3J 7.1, CH2), 1.40 (3H, t, 3J 7.1, CH3),
(400 MHz; CDCl3; Me4Si) 7.26 (1H, dd, J3,5 1.3, J3,4 5.0, H3), 7.08
3
3
3
4
(1H, dd, J4,3 3.7, J4,5 5.0, H4), 7.28 (1H, dd, J5,4 5.0, J5,3 1.3, H5),
4
4
7.69 (1H, d, J2 ,4 1.3, H20), 8.35 (1H, d, J4 ,2 1.3, H40), 5.20 (2H, q,
3J7.0, CH2), 1.69 (3H, t, 3J 7.0, CH3). d13C(100.613 MHz; CDCl3; Me4-
Si) 316.82(Ccarb), 223.2 (COtrans), 217.0 (COcis), 137.7 (C2), 124.9
(C3), 124.0 (C4), 128.0 (C5), 128.5 (C20), 138.0 (C30), 137.3 (C40),
155.6 (C50), 76.2 (CH2), 15.2 (CH3).
0
0
0
0
4.36 (2H, q, 3J 7.1, CH2), 1.36 (3H, t, 3J 7.1, CH3).
d
13C
(100.613 MHz; CDCl3; Me4Si) 289.9 (Ccarb), 202.6 (COtrans), 197.5
0
0
(COcis), 161.1, (CO(2 )), 161.0 (CO(5 )), 145.3 (C2), 130.7 (C3), 141.7
(C4), 157.9 (C5), 133.4 (C20), 137.1 (C30), 135.3 (C40), 138.2 (C50),
78.5 (CH2 (carbene)), 62.1 (CH2 (ester)), 15.0 (CH3), 14.2 (CH3),
14.1 (CH3). 689.9851 g/mol, 689.9951 (33%, [M]ꢁ), 662.0050 (29%,
5b: Yield: 0.017 g (0.04 mmol, 2%), orange brown crystals.
m
CO(hexane)/cmꢁ1 2057 m (A1(1)), 1980sh (A(12)), 1958 s (E). d1H