10.1002/ejic.201900242
European Journal of Inorganic Chemistry
FULL PAPER
1H NMR (400 MHz, CD3CN, 300 K): = 7.77 (s, 2 H, Cpz-H3), 7.64 (s, 2 H,
Cpz-H5), 6.60-6.26 (m, 2 H, Cpz-H4), 5.07 (s, 4 H, Npz-CH2), 2.59 (s, 2 H,
CH2-CH2-CH3), 1.96 (s, 6 H, CH3CN), 1.45 (dd, 2 H, 3J = 13.6, 7.5 Hz, CH2-
CH2-CH3), 0.83 (t, 3J = 7.2 Hz, 3 H, CH2-CH2-CH3) ppm. 13C NMR (101
MHz, CD3CN, 300 K): = 141.5 (Cpz-3), 132.9 (Cpz-5), 118.3 (CH3CN),
107.4 (Cpz-4), 67.9 (Npz-CH2), 52.5 (CH2-CH2-CH3), 21.2 (CH2-CH2-CH3),
11.5 (CH2-CH2-CH3), 1.62 (CH3CN) ppm. C15H23ClCuN7O4 (464.4): calcd.
C 38.80, H 4.99, N 21.11; found C 38.84, H 4.93, N 20.85.
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[Cu(2a)]PF6 (9a)
Tetrakis(acetonitrile)copper(I) hexafluoridophosphate (194 mg, 0.521
mmol) was dissolved in 3 mL dry acetonitrile and a 5 mL solution of 2a
(107 mg, 0.521 mmol) in dry acetonitrile was slowly added via a syringe.
The colorless solution was stirred for 30 min at room temperature and the
solvent evaporated under reduced pressure. The desired product was
obtained as a colorless solid (171 mg, 0.413 mmol, 79 %). IR (ATR):
ν̃ = 3315 (w), 3152 (w), 2905 (w), 2870 (w), 1519 (w), 1449 (w), 1439 (w),
1416 (m), 1380 (w), 1335 (w), 1296 (m), 1271 (w), 1208 (w), 1180 (w),
1126 (w), 1104 (w), 1073 (m), 1016 (w), 920 (w), 822 (vs), 761 (s), 643
(m), 555 (s) cm-1. 1H NMR (400 MHz, CD3CN, 300 K): = 7.60-7.59 (m,
4 H, Cpz-H3, Cpz-H5), 6.34 (t, 3J = 2.2 Hz, 2 H, Cpz-H4), 4.21-4.19 (m, 4 H,
Npz-CH2-CH2-NH), 3.00-2.97 (m, 4 H, Npz-CH2-CH2-NH) ppm. 13C NMR
(101 MHz, CD3CN, 300 K): = 141.0 (Cpz-3), 132.2 (Cpz-5), 106.3 (Cpz-4),
51.4 (Npz-CH2-CH2), 50.8 (NH-CH2-CH2) ppm. C10H15CuF6N5P (413.8):
calcd. C 29.03, H 3.65, N 16.93; found C 29.21, H 3.73, N 16.77.
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Complex 9b was prepared in the same manner as described for 9a using
Tetrakis(acetonitrile)copper(I) hexafluoridophosphate (150 mg, 0.513
mmol) and 2b (105 mg, 0.402 mmol). The desired product was obtained
as a colorless solid (153 mg, 0.326 mmol, 81 %). IR (ATR): ν̃ = 3307 (w),
2933 (w), 2874 (w), 1551 (w), 1463 (m), 1437 (w), 1423 (w), 1390 (m),
1312 (w), 1231 (w), 1122 (w), 1057 (w), 1033 (w), 930 (w), 831 (vs), 741
(m), 620 (w), 555 (s) cm-1. 1H NMR (400 MHz, CD3CN, 300 K): = 5.95 (s,
2 H, Cpz-H4), 3.95-3.97 (m, 4 H, Npz-CH2-CH2-NH), 2.99 (s, 4 H, Npz-CH2-
CH2-NH), 2.26 (s, 6 H, Cpz3-CH3), 2.22 (s, 6 H,Cpz5-CH3) ppm. 13C NMR
(101 MHz, CD3CN, 300 K): = 148.8 (Cpz-3), 141.8 (Cpz-5), 105.9 (Cpz-4),
50.5 (Npz-CH2-CH2), 47.2 (NH-CH2-CH2), 14.2 (Cpz3-CH3) 11.4 (Cpz5-CH3)
ppm. C14H23CuF6N5P (469.9): calcd. C 35.79, H 4.93, N 14.90; found C
35.82, H 5.05, N 14.90.
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Acknowledgements
The authors thank S. Pehlke and J. Pick for the spectroscopic
measurements as well as I. Jeß for the measurement of the
crystals and the CAU Kiel for financial support of this research.
Keywords: Tyrosinase • enzyme models• coordination modes •
pyrazolic compounds • homogeneous catalysis • N-donor
ligands
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