Synthesis, structure and redox properties of bis(cyclopentadienyl)dithiolene complexes of molybdenum and tungsten.

The compounds [Cp(2)M(S(2)C(2)(H)R)] (M = Mo or W; R = phenyl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl or quinoxalin-2-yl) and [Cp(2)Mo(S(2)C(2)(Me)(pyridin-2-yl)] have been prepared by a facile and general route for the synthesis of dithiolene complexes, viz. the reaction of [Cp(2)MCl(2)] (M = Mo or W) with the dithiolene pro-ligand generated by reacting the corresponding 4-(R)-1,3-dithiol-2-one with CsOH. These Mo compounds were reported previously (Hsu et al., Inorg. Chem. 1996, 35, 4743); however, the preparative method employed herein is more versatile and generates the compounds in good yield and all of the W compounds are new. Electrochemical investigations have shown that each compound undergoes a diffusion controlled one-electron oxidation (OX(I)) and a one-electron reduction (RED(I)) process; each redox change occurs at a more positive potential for a Mo compound than for its W counterpart. The mono-cations generated by chemical or electrochemical oxidation are stable and the structures of both components of the [Cp(2)Mo(S(2)C(2)(H)R)](+)/[Cp(2)Mo(S(2)C(2)(H)R)] (R = Ph or pyridin-3-yl) redox couples have been determined by X-ray crystallography. For each redox related pair, the changes in the Mo-S, S-C and C-C bond lengths of the {MoSCCS} moiety are generally consistent with OX(I) involving the loss of an electron from a π-orbital that is Mo-S and C-S antibonding and C-C bonding in character. These results have been interpreted successfully within the framework provided by DFT calculations accomplished for [Cp(2)M(S(2)C(2)(H)Ph)](n) (M = Mo or W; n = +1, 0 or -1). The HOMO of the neutral compounds is derived mainly from the dithiolene π(3) orbital (65%); therefore, OX(I) is essentially a dithiolene-based process. The similarity of the potentials for OX(I) (ca. 30 mV) for analogous Mo and W compounds is consistent with this interpretation and the EPR spectra of each of the Mo cations show that the unpaired electron is coupled to the dithiolene proton but relatively weakly to (95,97)Mo. The DFT calculations indicate that the unpaired electron is more localised on the metal in the mono-anions than in the mono-cations. In agreement with this, the EPR spectrum of each of the Mo-containing mono-anions manifests a larger (95,97)Mo coupling (A(iso)) than observed for the corresponding mono-cation and RED(I) for a W compound is significantly (ca. 300 mV) more negative than that of its Mo counterpart. [Cp(2)W(S(2)C(2)(H)(quinoxalin-2-yl))] is anomalous; RED(I) occurs at a potential ca. 230 mV more positive than expected from that of its Mo counterpart and the EPR spectrum of the mono-anion is typical of an organic radical. DFT calculations indicate that these properties arise because the electron is added to a quinoxalin-2-yl π-orbital.

A crystallographic, EPR and theoretical study of the Jahn-Teller distortion in [CuTp2] (Tp- = tris[pyrazol-1-yl]hydridoborate).

Crystals of the title compound (1) contain two independent, centrosymmetric half-molecules per asymmetric unit. While both of these show Jahn-Teller elongated six-coordinate geometries, the lengths of the elongated Cu-N bonds in the two molecules differ by 0.117(2) A at 30 K. The structure of one of these molecules (molecule A) does not vary with temperature below 350 K. The other molecule (molecule B) shows Cu-N bond lengths that are temperature-dependent between 225 and 375 K, but do not vary further at lower temperature. This indicates a fluxional axis of Jahn-Teller elongation in this molecule at these higher temperatures. Consideration of the thermal parameters in these structures implies that the fluxionality in molecule B is frozen out near 150 K. This conclusion is supported by a Q-band powder EPR study. The d-d transition energies of molecules A and B have been calculated by several density function (DF) methods, including a time-dependent DF calculation. The crystallographic data have been reproduced using the vibronic coupling model of Burgi and Hitchman. This has shown that the different fluxionality regimes for molecules A and B are not a consequence of their different static molecular structures, but rather reflect their different local environments in the crystal.

Ni(III) vs. Ni(II)-thiyl radical: charge-delocalisation in a binuclear Ni(III)Ni(II)-dithiolate complex.

Multi-frequency EPR spectroscopy on 61Ni-labelled samples of [Ni2(L)]3+ confirms extensive charge-delocalisation between the Ni(III) centre and thiolate donors in the Ni(II)Ni(III) complex.

Detection and measurement of noncoincidence between the principal axes of the g-matrix and zero-field splitting tensor using multifrequency powder EPR spectroscopy: application to cis-[(NH(3))(2)Pt(1-MeU)(2)Cu(H(2)O)(2)](SO(4)) x 4.5H(2)O (1-MeU = monoanion of 1-methyluracil).

Multifrequency continuous wave EPR spectra (4-34 GHz) on a powder of the title compound are consistent with a spin-triplet state. This arises from interaction between centrosymmetrically related pairs of copper(II) ions in the solid. The spectra at all frequencies have been simulated with a single set of spin-Hamiltonian parameters. The results show that there is noncoincidence between the principal axes of the g-matrices on each copper center and those of the zero-field splitting (D) tensor. This noncoincidence is a single rotation of 33 degrees +/- 2 degrees. The parameters from the powder spectra have been verified by a subsequent single-crystal EPR study which yielded the spin-Hamiltonian parameters g(XX) = 2.074, g(YY) = 2.093, g(ZZ) = 2.385, D(XX) = +/-0.0228 cm(-1), D(YY) = +/-0.0211 cm(-1), D(ZZ) = -/+0.0439 cm(-1) with Euler angles of alpha = 179 degrees, chi = 33.4 degrees, and gamma = 328 degrees. Analysis of the zero-field splitting tensor in terms of exchange indicates that the interaction between the pairs of copper(II) ions is almost entirely dipolar in origin. This study shows that multifrequency EPR spectroscopy on powders, coupled with spectrum simulation, can detect and measure noncoincidence between the principal axes of the g-matrix and zero-field splitting tensor, and does not necessarily require the presence of metal hyperfine interactions.

Steric Control of the Electronic Ground State in Six-Coordinate Copper(II) Complexes.

Replacing the 3- and 3''-protons of the ligand 2,6-di(pyrazol-1-yl)pyridine L by mesityl groups changes the electronic ground state of [Cu(L)2 ]2+ complexes from {d x 2-y 2}1 to {d z 2}1 . This is the best example so far for a "homoleptic" Jahn-Teller-compressed six-coordinate CuII complex.