RESUMO
In this paper are presented the syntheses, characterizations, and dynamic solution behaviors of three cis-[Ru(bpy)2(L)2] (bpy = 2,2'-bipyridine) complexes, 1-3, in which L represents the monodentate ligands 1-methylimidazole (MeIm), 1,2-dimethylimidazole (Me2Im), and 1-methylbenzimidazole (MeBim), respectively. Because of their different steric properties, these three monodentate ligands yield complexes that show quite different fluxional behaviors in solution. These behaviors are studied with several 1H NMR techniques at various temperatures between -95 and degrees C. The 1H NMR spectra of 1, which has the smallest monodentate ligand of the three used, indicate the complex to be in fast exchange (i.e., the imidazoles rotate around their Ru-N axes) at all recording temperatures. The sterically more demanding ligands, Me2Im and MeBim, in 2 and 3, respectively, are in fast exchange at 55 degrees C and in slow exchange at low temperatures, showing three different atropisomers: two head-to-tail (HT) isomers and one head-to-head (HH) isomer. The newly synthesized bidentate ligand 1,2-bis-(1-methyl-2-benzimidazolyl)ethane (mdbz) forms the complex cis-[Ru(bpy)2(mdbz)](PF6)2 (4), in which the two benzimidazole moieties are constrained and relatively fixed. The two tethered benzimidazoles in 4 cannot rotate around their Ru-N axes, and therefore 4 is a good model for the main HT isomer of 3.
RESUMO
The synthesis and characterization of alpha-[Ru(azpy)2(NO3)2], 1, are reported (azpy is 2-(phenylazo)pyridine; alpha indicates the isomer in which the coordinating pairs ONO2, N(py), and N(azo) are cis, trans, and cis, respectively). The solid-state structure of 1 has been determined by X-ray crystallography. Crystal data: orthorhombic a = 15.423(5) A, b = 14.034(5) A, c = 10.970(5) A, V = 2374(2) A3, space group P2(1)2(1)2(1) (No. 19), Z = 4, Dcalc = 1.655 g cm-3. The structure refinement converged at R1 = 0.042 and wR2 = 0.118 for 3615 unique reflections and 337 parameters. The octahedral complex shows monodentate coordination of the two nitrate ligands. The Ru-N(azo) bond distances (2.014(4) and 1.960(4) A), slightly shorter than the Ru-N(py) bonds (2.031(4) and 2.059(4) A), agree well with the pi-back-bonding ability of the azo groups. The binding of the DNA-model bases 9-ethylguanine (9egua) and guanosine (guo) to 1 has been studied and compared with previously obtained results for the binding of model bases to the bis(bipyridyl)ruthenium(II) complex. The ligands 9egua and guo appear to form monofunctional adducts, which have been isolated as alpha-[Ru(azpy)2(9egua)Cl]PF6, 2, alpha-[Ru(azpy)2(9egua)(H2O)]-(PF6)2, 3, alpha-[Ru(azpy)2(guo)(H2O)](PF6)2, 4, and alpha-[Ru(azpy)2(guo)Cl]Cl, 5. The orientations of 9egua and guo in these complexes have been determined in detail with the use of 2D NOESY NMR spectroscopy. In 2 and 5, H8 is directly pointed toward the coordinated Cl, whereas, in 3 and 4, H8 is wedged between the pyridine and phenyl rings. The guanine derivatives in the azpy complexes can have more orientations than found for related cis-[Ru(bpy)2Cl2] species. This fluxionality is considered to be important in the binding of the alpha-bis(2-(phenylazo)pyridine)ruthenium(II) complex to DNA. In complex 1, ruthenium is the chiral center and in the binding to guanosine, two diastereoisomers each of adducts 4 and 5 have been clearly identified by NMR spectroscopy.
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The reaction of Haat [Haat = (3-acetylamino-1,2,4-triazole)] with aquated Cu(CF3SO3)2, Cu(NO3)2, and Cu(ClO4)2, respectively, in water results in the trinuclear complexes [Cu3(OH)(aat)3(CF3SO3)(H2O)2](CF3SO3) (1), [Cu3(OH)(aat)3(NO3)(H2O)2](NO3).(H2O)2 (2), and [Cu3(OH)(aat)3(ClO4)(H2O)2](ClO4) (3). The synthesis, X-ray structure, and magnetic and spectroscopic properties of the three title complexes are described. The cation of the three complexes is trinuclear with a Cu3OH skeleton which has the N-N diazine grouping of a triazole ring as bridge between each pair of copper atoms. The Cu3OH units have an average Cu-O distance of 1.991(6) (1), 2.000(6) (2), and 2.007(6) (3) A, an average Cu-Cu' distance of 3.355(2) (1), 3.341(1) (2), and 3.371(3) (3) A, and an average Cu-O-Cu' angle of 114.6(3) degrees (1), 112.4(2) degrees (2), and 115.4(3) degrees (3). The existence of the Cu3OH fragment is confirmed by a pseudotetrahedral oxygen environment, by detection of the OH hydrogen atom, and by stoichiometry. In the trinuclear unit the metal ions show, in the first approximation, a pseudo-square-planar pyramidal environment forming a CuN2O3 chromophore; three of the basal positions are occupied by N,N,O aat ligand atoms, the fourth one is occupied by the oxygen of the central OH group, and the apical site is occupied by an oxygen atom from a water molecule in the case of two of the copper(II) atoms and by an oxygen atom from the coordinating anion in the case of the third metal ion. The three compounds exhibit strong antiferromagnetic interaction, with similar J constants [J = -197.7 (1), J = -190.9 (2), J = -198.2 (3) cm-1], reaching complete spin coupling at ca. 75 K (1)/55 K (2)/95 K (3). At very low temperature the magnetic moment (magnetic susceptibility) falls below that expected for one unpaired electron. Magnetic parameters are discussed on the basis of the structural results and compared with those reported in the literature for related trimeric Cu(II) compounds with N-O or N-N peripheral bridges. Solid state EPR spectra of the three complexes recorded at liquid N temperature show axial signals. Crystal data: C14H20Cu3F6N12O12S2 (1) (Mw = 917.16) crystallizes in the monoclinic space group, P2(1)/c, Z = 4, with cell dimensions a = 13.080(2) A, b = 17.202(2) A, c = 13.840(2) A, beta = 92.40(1) degrees, and V = 3111.3(7) A3, Dcalcd = 1.958 Mg m-3; the final agreement values were R1 = 0.0582 and wR2 = 0.1462 for 7107 unique reflections. C12H24Cu3N14O14 (2) (Mw = 779.07) crystallizes in the triclinic space group, P1, Z = 2, with cell dimensions a = 9.647(2) A, b = 9.985(2) A, c = 15.314(2) A, alpha = 84.080(10), beta = 87.694(10), gamma = 65.030(10) degrees, and V = 1330.1(4) A3, Dcalcd = 1.945 Mg m-3; the final agreement values were R1 = 0.0397 and wR2 = 0.0950 for 7728 unique reflections. C12H20Cl2Cu3N12O14 (3) (Mw = 817.92) crystallizes in the monoclinic space group, P2(1)/a, Z = 4, with cell dimensions a = 14.238(5) A, b = 16.387(6) A, c = 11.678(4) A, gamma = 90.45(2) degrees, and V = 2724.6(18) A3, Dcalcd = 1.994 Mg m-3; the final agreement values were R1 = 0.0616 and wR2 = 0.1279 for 4038 unique reflections.
RESUMO
The structure of the coordination compound [Fe(teec)(6)](BF(4))(2), hexa[1-(2-chloroethyl)tetrazole]iron(II) di(borotetrafluoride), has been determined using the grid-search techniques of the program suite MRIA. A Guinier-camera data set was used to determine the unit cell, the space group and to position the initial model. A high-resolution synchrotron powder data set was used to position a more detailed model using torsion-angle variation and to refine the structure leading to Rp = 0.0689, Rw = 0.0805 and GoF = 1.38. The crystal structure at room temperature shows the existence of two symmetry-equivalent iron(II) ions in the high-spin state.
RESUMO
[Fe(btzp)3](ClO4)2 (btzp = 1,2-bis(tetrazol-1-yl)propane) represents the first structurally characterized Fe(II) linear chain compound exhibiting thermal spin crossover. It shows a very gradual spin transition (T1/2 = 130 K) which has been followed by magnetic susceptibility measurements and 57Fe Mössbauer spectroscopy. The structure has been solved at 200 and 100 K by single-crystal X-ray analysis. It crystallizes in the trigonal space group P3c1 with Z = 2 Fe(II) units at both temperatures. The molecular structure consists of chains running along the c axis in which the Fe(II) ions are linked by three N4,N4' coordinating bis(tetrazole) ligands. The main difference between the two forms appears to be in the Fe-N bond lengths, which are 2.164(4) A at 200 K and 2.038(4) A at 100 K. The Fe-Fe separations are 7.422(1) A at 200 K and 7.273(1) A at 100 K. The EXAFS results are consistent with the crystal structure. In both spin states, the FeN6 octahedron is almost regular within the EXAFS resolution. The Fe-N distance is found as 2.16(2) A at 300 K and 2.00(2) A at 40 K. The absence of the "7 A peak" in the EXAFS spectra of [Fe(btzp)3](ClO4)2, in contrast with what has been observed for the [Fe(4-R-1,2,4-triazole)3]-(anion)2 chain compounds, confirms that this peak can be used as the signature of a metal alignment only when it involves a strongly enhanced multiple scattering M-M-M path, with M-M spacing less than 4 A. Irradiation with green light at 5 K has led to the population of the metastable high-spin state for the iron(II) ion. The nature of the spin-crossover behavior has been discussed on the basis of the structural features.