Crystallographic, Electrochemical, and Pulsed EPR Study of Copper(II) Polyimidazole Complexes Relevant to the Metal Sites of Copper Proteins(,).

Copper(II) complexes of the following polyimidazole ligands have been synthesized: bis(imidazol-2-yl)methane (BIM), bis(imidazol-2-yl) ketone (BIK), 4-(imidazol-4-ylmethyl)-2-(imidazol-2-ylmethyl)imidazole (TRIM), bis[4-(imidazol-4-ylmethyl)imidazol-2-yl]methane (TIM), and bis[4-(imidazol-4-ylmethyl)imidazol-2-yl] ketone (TIK). Their crystal structures have been determined using X-ray diffraction. [Cu(ClO(4))(2)(BIM)(2)], 1, belongs to the triclinic space group P&onemacr; system, a = 7.161(4) Å, b = 7.986(6) Å, c = 9.865(3) Å, alpha = 76.73(5) degrees, beta = 71.18(3) degrees, gamma = 76.44(5) degrees, Z = 1, T = 291 K; R = 0.035, R(w) = 0.036 for 1668 reflections; Cu-N = 1.998(3) and 2.001(2) Å, Cu-O = 2.574(4) Å, in a tetragonal geometry. Cu(BIK)(2)(2), 2, belongs to the monoclinic space group C2/c system, a = 9.029(3) Å, b = 12.497(2)Å, c = 19.197(2) Å, beta = 94.59(2) degrees, Z = 4, T = 291 K; R = 0.056, R(w) = 0.061 for 1052 reflections; Cu-N = 1.961(7) and 1.954(7) Å, in a distorted tetrahedral geometry. [CuCl(TRIM)(CH(3)OH)]Cl, 6, belongs to the monoclinic space group P2(1)/n system, a = 14.192(5) Å, b = 13.832(5) Å, c = 7.913(3) Å, beta = 90.55(4) degrees, Z = 4, T = 291 K; R = 0.062, R(w) = 0.057 for 1377 reflections; Cu-N = 1.987(7), 2.007(7) and 2.007(6) Å, Cu-O = 2.521(7) Å, Cu-Cl = 2.298(2) Å, in a square pyramidal geometry. Cu(ClO(4))(TIM), 4, belongs to the triclinic space group P&onemacr; system, a = 9.604(4) Å, b = 11.508(6) Å, c = 12.003(8) Å, alpha = 58.79(4) degrees, beta = 94.59(2) degrees, gamma = 67.43(3) degrees, Z = 2, T = 291 K; R = 0.057, R(w) = 0.062 for 2084 reflections; Cu-N = 1.985(7), 1.964(7), 1.967(7), and 1.966(7) Å, Cu-O = 2.553(8) Å, in a distorted square pyramidal geometry. CuCl(TIK), 7, belongs to the triclinic space group P&onemacr; system, a = 7.432(3) Å, b = 12.573(3) Å, c = 12.945(2) Å, alpha = 114.94(4) degrees, beta = 92.46(2) degrees, gamma = 103.49(3) degrees, Z = 2, T = 291 K; R = 0.043, R(w) = 0.049 for 2305 reflections; Cu-N = 1.984(5), 1.989(5), 2.012(5), and 1.979(5) Å, Cu-Cl = 2.796(2) Å, in a distorted bipyramidal geometry. In methanol solution, the perchlorato complexes 1, 2, Cu(TRIM)(ClO(4))(2) (3), 4, and Cu(TIK)(ClO(4))(2) (5) exhibited redox potentials from -215 to +284 mV vs NHE together with a visible absorption from 604 to 728 nm. Electron spin-echo envelope modulation (ESEEM) spectroscopy data, particularly the nuclear quadrupole interaction (NQI) parameters e(2)qQ and eta of the remote nitrogen (N1H), were analyzed and interpreted according to the model devised by Jiang et al. (J. Am. Chem. Soc. 1990, 112, 9035) with reference to Cu(HIm)(4)(ClO(4))(2). The results are the following: (i) C2 substitution of the imidazole ring, next to the remote nitrogen (1, 2) decreases the asymmetry parameter eta to ca. 0.75 compared to 1.00 for Cu(HIm)(4)(ClO(4))(2); this effect of C2 substitution on the symmetry of the electric field gradient at N1H appears similar for both the electron-donating methylene substituents (1) and the electron-withdrawing carbonyl group (2). (ii) The electron-donating or -withdrawing properties of the substituent are reflected by the variation of the e(2)qQ parameter, increasing from 1.43 to 1.75 MHz (1) or decreasing to 1.38 MHz (2), and by the nu(+) transition shifting toward higher frequencies from 1.49 to 1.65 MHz (1, 3, 4) or to lower frequencies to 1.29 MHz (2, 5). The use of the eta and nu(+) parameters to assign the Ndelta vs Nepsilon coordination of histidine to the metal and to detect modified histidine in copper-binding proteins is discussed.