6: Color: red powder. Yield: 79% (257 mg, 0.28 mmol). IR (ATR): ν = 3068 (w, CH), 2045 (vs, N3),
-1 1
2
007 (vs, C≡O), 1928 (vs, C≡O), 1897 (vs, C≡O), 1610 (s, CC/CN), 1429, 788 cm . H NMR ([D ]
6
DMSO, 400.40 MHz): δ = 9.20 (d, 3JH,H = 6.0 Hz, 1H), 9.13 (s, 1H), 9.06 (d, 3JH,H = 8.1 Hz, 1H), 8.83
(
d, 3JH,H = 4.3 Hz, 1H), 8.44 (s, 2H), 8.32 (m, 2H), 8.11 (m, 1H), 8.04 (m, 1H), 7.77 (m, 1H), 7.66 (m,
1
3
1
1
H) ppm. C NMR ([D ] DMSO, 100.68 MHz): δ = 162.7, 161.6, 157.8, 156.8, 156.3, 152.9, 152.4,
6
49.2, 149.1, 146.3, 139.3, 137.3, 137.0, 128.7, 126.5, 125.2, 125.1, 124.7, 124.3, 124.0, 119.7
+
+
ppm. ESI-MS (positive mode, acetone): m/z = 860.0589 {[M–N ]} , 808.0639 {[M–2CO–N +2H]} ,
3
3
+
6
2
27.1321 {[LDTP +Mn+CO+2H]} . C H Mn N O ·2H O: C 53.74, H 3.01, N 17.91; found C 53.72, H
4
2
24
2
12
6
2
.63, N 17.29.
Synthesis of 7–9
,4,4-trifluoro-2-butynoic acid ethyl ester (166 mg, 1 mmol) was added to the acetone solution
3
8
4
of the azide complexes (0.2 mmol, 100 mg (4); 115 mg (5), 180 mg (6)) and the reaction mixtures
were stirred at room temperature for 5 d. For 7 and 8, the solvent was removed under vacuum
and the orange precipitate was washed with diethyl ether and dried in vacuo. Complex 9 was
precipitated from the reaction mixture, washed with acetone, diethyl ether and dried.
7
2
7
8
4
: Color: orange powder. Yield: 82% (109 mg, 0.16 mmol). IR (ATR, diamond): ν = 3080 (w, CH),
031 (vs, C≡O), 1949 (vs, C≡O), 1912 (vs, C≡O), 1704 (s, C=O), 1524, 1472, 1234, 1193, 1137, 1055,
-1
1
3
78 cm . H NMR (CDCl , 500.12 MHz): δ = 9.34 (d, J = 3.8 Hz, 1H), 8.85 (m, 3H), 8.29 (m, 1H),
3
H,H
.17 (br, 1H), 8.05 (br, 1H), 7.92 (m, 3H), 7.76 (d, 3JH,H = 9.1 Hz, 1H), 7.55 (m, 2H), 7.46 (m, 1H),
.22 (q, 3JH,H = 7.1 Hz, 2H, CH ), 1.25 (t, J = 7.2 Hz, 3H, CH ) ppm. C NMR (CDCl , 125.75 MHz):
3
13
2
H,H
3
3
δ = 222.4 (C≡O), 218.7 (C≡O), 215.7 (C≡O), 164.6 (C=O), 161.2, 158.7, 157.2, 157.1, 153.7, 151.9,
2
1
1
50.4, 149.5, 148.8, 139.1 (q, J = 37.8 Hz, C-CF ), 138.6, 137.5, 137.3, 137.0, 126.1, 125.5, 125.2,
C,F
3
1
19
25.0, 124.5, 123.0, 121.8 (q, J = 265.2 Hz, CF ), 121.6, 118.5, 60.4 (CH ), 14.0 (CH ) ppm. F
C,F
3
2
3
NMR (CDCl , 470.6 MHz): δ = –59.8 (CF ) ppm. ESI-MS (positive mode, acetone): m/z = 696.0408
3
3
{
[M+K]}+,
680.0671
{[M+Na]}+,
658.0852
{[M+H]}+,
449.0442
{[M–triazolate]}+.
C H F MnN O ·0.5H O: C 52.26, H 3.02, N 14.71, found, C 52.55, H 2.82, N 13.81.
2
9
19
3
7
5
2
8
2
1
: Color: orange powder. Yield: 76% (113 mg, 0.15 mmol). IR (ATR, diamond): ν = 2977 (w, CH),
865 (w, CH), 2029 (vs, C≡O), 1927 (vs, C≡O), 1727 (s, C=O), 1598 (s, CC/CN), 1525, 1432, 1255,
-1 1
122, 1030, 928, 790 cm . H NMR (CDCl , 500.12 MHz): δ = 9.30 (1H), 8.87 (1H), 7.90 (2H), 7.79
3
(
3H), 7.54 (2H), 7.0 (2H), 4.22 (2H, CH ), 3.92 (4H, morphine), 3.32 (4H, morphine), 1.27 (3H, CH )
2
3
1
3
ppm (some aromatic signals are overlapped with the solvent signal). C-NMR (CDCl , 125.75 MHz):
3