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J Krzystek

Publications and source records attributed to J Krzystek.

At least 19 recordsLinked to original sources

Electronic structure of four-coordinate C3v nickel(II) scorpionate complexes: investigation by high-frequency and -field electron paramagnetic resonance and electronic absorption spectroscopies.

A series of complexes of formula TpNiX, where Tp*- = hydrotris(3,5-dimethylpyrazole)borate and X = Cl, Br, I, has been characterized by electronic absorption spectroscopy in the visible and near-infrared (NIR) region and by high-frequency and -field electron paramagnetic resonance (HFEPR) spectroscopy. The crystal structure of TpNiCl has been previously reported; that for TpNiBr is given here: space group = Pmc2(1), a = 13.209(2) A, b = 8.082(2) A, c = 17.639(4) A, alpha = beta = gamma = 90 degrees , Z = 4. TpNiX contains a four-coordinate nickel(II) ion (3d8) with approximate C3v point group symmetry about the metal and a resulting S = 1 high-spin ground state. As a consequence of sizable zero-field splitting (zfs), TpNiX complexes are "EPR silent" with use of conventional EPR; however, HFEPR allows observation of multiple transitions. Analysis of the resonance field versus the frequency dependence of these transitions allows extraction of the full set of spin Hamiltonian parameters. The axial zfs parameter for TpNiX displays pronounced halogen contributions down the series: D = +3.93(2), -11.43(3), -22.81(1) cm(-1), for X = Cl, Br, I, respectively. The magnitude and change in sign of D observed for TpNiX reflects the increasing bromine and iodine spin-orbit contributions facilitated by strong covalent interactions with nickel(II). These spin Hamiltonian parameters are combined with estimates of 3d energy levels based on the visible-NIR spectra to yield ligand-field parameters for these complexes following the angular overlap model (AOM). This description of electronic structure and bonding in a pseudotetrahedral nickel(II) complex can enhance the understanding of similar sites in metalloproteins, both native nickel enzymes and nickel-substituted zinc enzymes.

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Multi-frequency high-field EPR study of iron centers in malarial pigments.

The multi-frequency high-field electron paramagnetic resonance (HFEPR) was used to study the magnetic properties of malarial pigment hemozoin and its synthetic analogue, beta-hematin. (FeIII-protoporphyrin-IX)2 dimers containing five-coordinate high-spin FeIII, S = 5/2, are the building blocks of these pigments. The fit of EPR spectra that were acquired in an unprecedented wide range of microwave frequencies of 34 and 94 GHz for hemozoin and 27-500 GHz for beta-hematin yielded a complete set of intrinsic spin Hamiltonian parameters: D = +5.85(1) cm-1, E = 0, g perpendicular = 1.95(1), g parallel = 2.00(1). These results point to the existence of largely axial symmetry of the iron environment in the bulk phase of hemozoin and beta-hematin.

Animals↗

Tunable-frequency high-field electron paramagnetic resonance.

A tunable-frequency methodology based on backward wave oscillator sources in high-frequency and -field EPR (HFEPR) is described. This methodology is illustrated by an application to three non-Kramers transition metal ion complexes and one Kramers ion complex. The complexes are of: Ni(II) (S=1) as found in dichlorobistriphenylphosphanenickel(II), Mn(III) (S=2) as found in mesotetrasulfonatoporphyrinatomanganese(III) chloride, Fe(II) (S=2) as found in ferrous sulfate tetrahydrate, and Co(II) (S=3/2) as found in azido(tris(3-tert-butylpyrazol-1-yl)hydroborate)cobalt(II). The above Ni(II) and Mn(III) complexes have been studied before by HFEPR using the multifrequency methodology based on Gunn oscillator sources, but not by the present method, while the Fe(II) and Co(II) complexes presented here have not been studied by any form of HFEPR. Highly accurate spin Hamiltonian parameters can be obtained by the experimental methodology described here, in combination with automated fitting procedures. This method is particularly successful in determining g-matrix parameters, which are very difficult to extract for high-spin systems from single frequency (or a very limited set of multi-frequency) HFEPR spectra, but is also able to deliver equally accurate values of the zero-field splitting tensor. The experimental methods involve either conventional magnetic field modulation or an optical modulation of the sub-THz wave beam. The relative merits of these and other experimental methods are discussed.

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Electron spin resonance in sine-gordon spin chains in the perturbative spinon regime.

We report the low-temperature multifrequency ESR studies of copper pyrimidine dinitrate, a spin-1/2 antiferromagnetic chain with alternating g tensor and the Dzyaloshinskii-Moriya interaction, allowing us to test a new theoretical concept proposed recently by Oshikawa and Affleck [Phys. Rev. Lett. 82, 5136 (1999)]. Their theory, based on bosonization and self-energy formalism, can be applied for precise calculation of ESR parameters of S=1/2 antiferromagnetic chains in the perturbative spinon regime. Excellent quantitative agreement between the theoretical predictions and experiment is obtained.

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Synthesis, characterization, and physicochemical properties of manganese(III) and manganese(V)-oxo corrolazines.

The structural and physicochemical properties of the manganese-corrolazine (Cz) complexes (TBP8Cz)Mn(V)O (1) and (TBP8Cz)Mn(III) (2) (TBP = p-tert-butylphenyl) have been determined. Recrystallization of 2 from toluene/MeOH resulted in the crystal structure of (TBP8Cz)Mn(III)(CH3OH) (2 x MeOH). The packing diagram of 2 x MeOH reveals hydrogen bonds between MeOH axial ligands and meso N atoms of adjacent molecules. Solution binding studies of 2 with different axial ligands (Cl-, Et3PO, and Ph3PO) reveal strong binding, corroborating the preference of the Mn(III) ion for a five-coordinate environment. High-frequency and field electron paramagnetic resonance (HFEPR) spectroscopy of solid 2 x MeOH shows that 2 x MeOH is best described as a high-spin (S = 2) Mn(III) complex with zero-field splitting parameters typical of corroles. Structural information on 1 was obtained through an X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) study and compared to XANES/EXAFS data for 2 x MeOH. The XANES data for 1 shows an intense pre-edge transition characteristic of a high-valent metal-oxo species, and a best fit of the EXAFS data gives a short Mn-O bond distance of 1.56 A, confirming the structure of the metal-oxo unit in 1. Detailed spectroelectrochemical studies of 1 and 2 were performed revealing multiple reversible redox processes for both complexes, including a relatively low potential for the Mn(V) --> Mn(IV) process in 1 (near 0.0 V vs saturated calomel reference electrode). Chemical reduction of 1 results in the formation of a Mn(III)Mn(IV)(mu-O) dimer as characterized by electron paramagnetic resonance spectroscopy.

Binding Sites↗

High-frequency and -field EPR investigation of a manganese(III) N-confused porphyrin complex, [Mn(NCTPP)(py)2].

We report the first high-frequency and -field electron paramagnetic resonance (HFEPR) study of a Mn(III) N-confused porphyrin (NCP) complex (NCP is also known as inverted porphyrin or 2-aza-21-carbaporphyrin). We have found a striking variation in the electronic properties of the S = 2 Mn(III) ion coordinated by NCP compared to other Mn(III) porphyrinoid complexes. Thus, inversion of a single pyrrole ring greatly changes the equatorial ligand field exerted and leads to large magnitudes of both the axial and rhombic zero-field splitting [respectively, D = -3.084(3) cm(-1), E = -0.608(3) cm(-1)], which are unprecedented in other Mn(III) porphyrinoids.

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Synthesis, crystal structure, and high-precision high-frequency and -field electron paramagnetic resonance investigation of a manganese(III) complex: [Mn(dbm)2(py)2](ClO4).

The complex [Mn(dbm)(2)(py)(2)](ClO(4)) (dbm = anion of 1,3-diphenyl-1,3-propanedione (dibenzoylmethane), py = pyridine) was synthesized and characterized by X-ray crystallography. It has tetragonally distorted geometry with the axial positions occupied by the py ligands and the equatorial positions by the dbm ligands. This mononuclear complex of high-spin Mn(III) (3d(4), S = 2) was studied by high-frequency and -field electron paramagnetic resonance (HFEPR) both as a solid powder and in frozen dichloromethane solution. Very high quality HFEPR spectra were recorded over a wide range of frequencies. The complete dataset of resonant magnetic fields versus transition energies was analyzed using automated fitting software. This analysis yielded the following spin Hamiltonian parameters (energies in cm(-1)): D = -4.504(2), E = -0.425(1), B(4)(0) = -1.8(4) x 10(-4), B(4)(2) = 7(3) x 10(-4), B(4)(4) = 48(4) x 10(-4), g(x) = 1.993(1), g(y) = 1.994(1), and g(z) = 1.983(1), where the B(4)(n) values represent fourth-order zero-field splitting terms that are generally very difficult to extract, even from single-crystal measurements. The results here demonstrate the applicability of HFEPR at high-precision measurements, even for powder samples. The zero-field splitting parameters determined here for [Mn(dbm)(2)(py)(2)](+) are placed into the context of those determined for other mononuclear complexes of Mn(III).

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High-frequency/high-field EPR spectroscopy of the high-spin ferrous ion in hexaaqua complexes.

Electron paramagnetic resonance (EPR) at conventional magnetic fields and microwave frequencies, respectively, B0 < or = 1.5 T, nu < or = 35 GHz, has been widely applied to odd electron-number (S = 1/2) transition metal complexes. This technique is less successfully applied to high-spin systems that have even electron configurations, e.g. Fe2+ (S = 2). The recently developed technique of high-frequency and high-field EPR (HFEPR), employing swept fields up to 25 T combined with multiple, sub-THz frequencies readily allows observation of EPR transitions in such high-spin systems. A parallel spectroscopic technique is frequency-domain magnetic resonance spectroscopy (FDMRS), in which the frequency is swept while at zero, or at discrete applied magnetic fields. We describe here the application of HFEPR and FDMRS to two simple high-spin (HS) ferrous (Fe2+) salts: ferrous perchlorate hydrate, [Fe(H2O)6](ClO4)2 and (NH4)2[Fe(H2O)6](SO4)2, historically known as ferrous ammonium sulfate. Both compounds contain hexaaquairon(II). The resulting spectra were analyzed using a spin Hamiltonian for S = 2 to yield highly accurate spin-Hamiltonian parameters. The complexes were also studied by powder DC magnetic susceptibility and zero-field Mössbauer effect spectroscopy for corroboration of magnetic resonance results. In the case of [Fe(H2O)6](ClO4)2, all the magnetic techniques were in excellent agreement and gave as consensus values: D = 11.2(2) cm(-1), E = 0.70(1) cm(-1). For (NH4)2[Fe(H2O)6](SO4)2, FDMRS and HFEPR gave D = 14.94(2) cm(-1), E = 3.778(2) cm(-1). We conclude that the spin-Hamiltonian parameters for the perchlorate best represent those for the isolated hexaaquairon(II) complex. To have established electronic parameters for the fundamentally important [Fe(H2O)6]2+ ion will be of use for future studies on biologically relevant systems containing high-spin Fe2+.

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Pseudooctahedral complexes of vanadium(III): electronic structure investigation by magnetic and electronic spectroscopy.

A variety of physical methods has been used to probe the non-Kramers, S = 1, V(III) ion in two types of pseudooctahedral complexes: V(acac)(3), where acac = anion of 2,4-pentanedione, and VX(3)(thf)(3), where thf = tetrahydrofuran and X = Cl and Br. These methods include tunable frequency and high-field electron paramagnetic resonance (HFEPR) spectroscopy (using frequencies of approximately 95-700 GHz and fields up to 25 T) in conjunction with electronic absorption, magnetic circular dichroism (MCD), and variable-temperature variable-field MCD (VTVH-MCD) spectroscopies. Variable-temperature magnetic susceptibility and field-dependent magnetization measurements were also performed. All measurements were conducted on complexes in the solid state (powder or mull samples). The field versus sub-THz wave quantum energy dependence of observed HFEPR resonances yielded the following spin Hamiltonian parameters for V(acac)(3): D = +7.470(1) cm(-1); E = +1.916(1) cm(-1); g(x) = 1.833(4); g(y) = 1.72(2); g(z) = 2.03(2). For VCl(3)(thf)(3), HFEPR detected a single zero-field transition at 15.8 cm(-1) (474 GHz), which was insufficient to determine the complete set of spin Hamiltonian parameters. For VBr(3)(thf)(3), however, a particularly rich data set was obtained using tunable-frequency HFEPR, and analysis of this data set gave the folowing: D = -16.162(6) cm(-1); E = -3.694(4) cm(-1); g(x) = 1.86(1); g(y) = 1.90(1); g(z) = 1.710(4). Analysis of the VTVH-MCD data gave spin Hamiltonian parameters in good agreement with those determined by HFEPR for both V(acac)(3) and VBr(3)(thf)(3) and in rough agreement with the estimate for VCl(3)(thf)(3) (D approximately 10 cm(-1), |E/D| approximately 0.18), together with the finding that the value of D is negative for both thf complexes. The electronic structures of these V(III) complexes are discussed in terms of their molecular structures and the electronic transitions observed by electronic absorption and MCD spectroscopies.

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Excitation hierarchy of the quantum sine-gordon spin chain in a strong magnetic field.

The magnetic excitation spectrum of copper pyrimidine dinitrate, a material containing S = 1 / 2 antiferromagnetic chains with alternating g tensor and the Dzyaloshinskii-Moriya interaction and exhibiting a field-induced spin gap, is probed using submillimeter wave electron spin resonance spectroscopy. Ten excitation modes are resolved in the low-temperature spectrum, and their frequency-field diagram is systematically studied in magnetic fields up to 25 T. The experimental data are sufficiently detailed to make a very accurate comparison with predictions based on the quantum sine-Gordon field theory. Signatures of three breather branches and a soliton, as well as those of several multiparticle excitation modes, are identified.

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High-frequency and -field EPR of a pseudo-octahedral complex of high-spin Fe(II): bis(2,2'-bi-2-thiazoline)bis(isothiocyanato)iron(II).

A pseudo-octahedral complex of high-spin Fe(II), bis(2,2'-bi-2-thiazoline)bis(isothiocyanato)iron(II), which has a cis-FeN'2N4 chromophore, has been investigated by high-frequency, high-field electron paramagnetic resonance (HFEPR). Complementary Mössbauer and DC magnetic susceptibility studies were also performed. HFEPR spectra of powder samples were recorded at frequencies up to 700 GHz and over a magnetic field range of 0-25 T. Analysis of the field-frequency data set yields the following set of spin Hamiltonian parameters for S = 2: D = +12.427(12) cm-1, E = +0.243(3) cm-1; gx = 2.147(3), gy = 2.166(3), gz = 2.01(1). The parameters are analyzed by use of a simple crystal-field model. This study represents the first precise determination by HFEPR of spin Hamiltonian parameters in six-coordinate high-spin Fe(II) and indicates the applicability of HFEPR to the study of high-spin Fe(II) in coordination complexes and biological model compounds.

Computer Simulation↗

Definitive spectroscopic determination of zero-field splitting in high-spin cobalt(II).

A high-spin Co(II) complex (3d(7), S = 3/2), Co(PPh(3))(2)Cl(2) (Ph = phenyl), has been investigated in the solid state by both high-frequency and -field electron paramagnetic resonance (HFEPR) and by variable-temperature, variable-field magnetic circular dichroism (VTVH-MCD). In HFEPR spectroscopy, the combination of variable sub-THz frequencies generated by backward wave oscillators (150-700 GHz, corresponding to energy 5-23 cm(-1)) and high magnetic fields (0-25 T) constitutes a novel experimental technique allowing accurate determination of a complete set of spin Hamiltonian parameters for this complex: D = -14.76(2) cm(-1), E = 1.141(8) cm(-1), g(x) = 2.166(4), g(y) = 2.170(4), g(z) = 2.240(5). Independent VTVH-MCD studies on multiple absorption bands of the complex yield D = -14(3) cm(-1), E = 0.96(20) cm(-1) (absolute value of E/D = 0.08(2)), g(x) = 2.15(5), g(y) = 2.16(4), and g(z) = 2.17(3). This very good agreement between HFEPR and MCD indicates that there is no inherent discrepancy between these two quite different experimental techniques. Thus, depending on the nature of the sample, either can be reliably used to determine zero-field splitting parameters in high-spin Co(II), with the HFEPR being more accurate but VTVH-MCD being more sensitive.

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High-frequency and -field EPR spectroscopy of tris(2,4-pentanedionato)manganese(III): investigation of solid-state versus solution Jahn-Teller effects.

High-frequency and -field electron paramagnetic resonance (HFEPR) spectroscopy of a classical coordination complex, Mn(acac)(3) (Hacac = 2,4-pentanedione), has been performed on both solid powder and frozen solution (in CH(2)Cl(2)/toluene, 3:2 v/v) samples. Parallel mode detection X-band EPR spectra exhibiting resolved (55)Mn hyperfine coupling were additionally obtained for frozen solutions. Magnetic susceptibility and field-dependent magnetization measurements were also made on powder samples. Analysis of the entire EPR data set for the frozen solution allowed extraction of the relevant spin Hamiltonian parameters: D = -4.52(2); |E| = 0.25(2) cm(-1); g(iso) = 1.99(1). The somewhat lower quality solid-state HFEPR data and the magnetic measurements confirmed these parameters. These parameters are compared to those for other complexes of Mn(III) and to previous studies on Mn(acac)(3) using X-ray crystallography, solution electronic absorption spectroscopy, and powder magnetic susceptibility. Crystal structures have been reported for Mn(acac)(3) and show tetragonal distortion, as expected for this Jahn-Teller ion (Mn(3+), 3d(4)). However, in one case, the molecule exhibits axial compression and, in another, axial elongation. The current HFEPR studies clearly show the negative sign of D, which corresponds to an axial (tetragonal) elongation in frozen solution. The correspondence among solution and solid-state HFEPR data, solid-state magnetic measurements, and an HFEPR study by others on a related complex indicates that the form of Mn(acac)(3) studied here exhibits axial elongation in all cases. Such tetragonal elongation has been found for Mn(3+) and Cr(2+) complexes with homoleptic pseudooctahedral geometry as well as for Mn(3+) in square pyramidal geometry. This taken together with the results obtained here for Mn(acac)(3) in frozen solution indicates that axial elongation could be considered the "natural" form of Jahn-Teller distortion for octahedral high-spin 3d(4) ions. The previous electronic absorption data together with current HFEPR and magnetic data allow estimation of ligand-field parameters for Mn(acac)(3).

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Direct observation of fine structure transitions in a paramagnetic nickel(II) complex using far-infrared magnetic spectroscopy: a new method for studying high-spin transition metal complexes.

Novel far-infrared (FIR) absorption spectroscopy in conjunction with multiple, fixed external magnetic fields (FIR magnetic spectroscopy, FIRMS) has been used to investigate pseudotetrahedral complexes with the formula M(PPh(3))(2)Cl(2) (M = Ni, Zn; Ph = C(6)H(5)). Crystal structures have been reported for the Ni complex; we report the structure of the Zn complex. Transmission spectra at 5 K of Ni(PPh(3))(2)Cl(2) (S = 1) at zero magnetic field exhibit absorption bands at 11.41, 15.28, and 23.0 cm(-1). The two lower frequency bands show great sensitivity to external magnetic field, and their field dependence is as expected for electron spin transitions allowing precise determination of the following parameters: |D| = 13.35(1) cm(-1), |E| = 1.93(1) cm(-1), g(x,y) = 2.20(1), g(z) = 2.00(1). Corresponding spectra of Zn(PPh(3))(2)Cl(2) (S = 0) exhibit bands only at >20 cm(-1), which show no field dependence. FIRMS is a promising technique for direct investigation of the electronic structure of high-spin transition metal complexes.

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Long-range ferromagnetic dipolar ordering of high-spin molecular clusters.

We report the first example of a transition to long-range magnetic order in a purely dipolarly interacting molecular magnet. For the magnetic cluster compound Mn6O4Br4(Et2dbm)6, the anisotropy experienced by the total spin S = 12 of each cluster is so small that spin-lattice relaxation remains fast down to the lowest temperatures, thus enabling dipolar order to occur within experimental times at T(c) = 0.16 K. In high magnetic fields, the relaxation rate becomes drastically reduced and the interplay between nuclear- and electron-spin lattice relaxation is revealed.

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High frequency and field EPR spectroscopy of Mn(III) complexes in frozen solutions.

We have performed high-frequency and -field electron paramagnetic resonance (HFEPR) experiments on two complexes of high-spin Mn(III) (3d(4),S=2): mesotetrasulfonato-porphyrinatomanganese(III) (Mn(TSP)) and [(R,R)-(-)-N,N(')-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III)] (Mn(salen)). The main aim of this work was to qualitatively and quantitatively characterize the conditions suitable for HFEPR of high-spin transition metal complexes in frozen solutions, and compare them with experiments performed on solid samples. Mn(TSP) is a porphyrin complex soluble in water, in contrast to most metalloporphyrins. Mn(salen), often referred to as Jacobsen's catalyst, is a complex widely used in organic synthesis for alkene epoxidation, and is soluble in organic solvents. High-quality HFEPR signals were observed for solid state Mn(TSP), as has been previously shown for many Mn(III) complexes. The present study is, however, the first to report high-quality HFEPR spectra of a Mn(III) complex in frozen aqueous solution. Analysis of the data yielded the following spin Hamiltonian parameters: S=2; D=-3.16+/-0.02 cm(-1), E=0, and isotropic g=2.00(2). No X-band EPR signals were observed for Mn(TSP), which is a consequence of this being a rigorously axial spin system. Mn(salen), in contrast, did not give good quality HFEPR spectra in the solid state, but high-quality HFEPR spectra were recorded in frozen organic solutions. Analysis of the data yielded the following spin Hamiltonian parameters: S=2; D=-2.47+/-0.02 cm(-1), |E|=0.17+/-0.01 cm(-1), and isotropic g=2.00(2). These values differ from those reported using X-band parallel mode EPR [J. Am. Chem. Soc. 123 (2001) 5710], as discussed in the text. Therefore, a comparison between HFEPR and parallel-mode X-band spectroscopy is made. Finally, the concentration sensitivity aspect of HFEPR spectroscopy is also discussed.

Electron Spin Resonance Spectroscopy↗

EPR spectra from "EPR-silent" species: high-frequency and high-field EPR spectroscopy of pseudotetrahedral complexes of nickel(II).

High-frequency and high-field electron paramagnetic resonance (HFEPR) spectroscopy (using frequencies of approximately 90-550 GHz and fields up to approximately 15 T) has been used to probe the non-Kramers, S = 1, Ni(2+) ion in a series of pseudotetrahedral complexes of general formula NiL(2)X(2), where L = PPh(3) (Ph = phenyl) and X = Cl, Br, and I. Analysis based on full-matrix solutions to the spin Hamiltonian for an S = 1 system gave zero-field splitting parameters: D = +13.20(5) cm(-1), /E/ = 1.85(5) cm(-1), g(x) = g(y) = g(z) = 2.20(5) for Ni(PPh(3))(2)Cl(2). These values are in good agreement with those obtained by powder magnetic susceptibility and field-dependent magnetization measurements and with earlier, single-crystal magnetic susceptibility measurements. For Ni(PPh(3))(2)Br(2), HFEPR suggested /D/ = 4.5(5) cm(-1), /E/ = 1.5(5) cm(-1), g(x) = g(y) = 2.2(1), and g(z) = 2.0(1), which are in agreement with concurrent magnetic measurements, but do not agree with previous single-crystal work. The previous studies were performed on a minor crystal form, while the present study was performed on the major form, and apparently the electronic parameters differ greatly between the two. HFEPR of Ni(PPh(3))(2)I(2) was unsuccessful; however, magnetic susceptibility measurements indicated /D/ = 27.9(1) cm(-1), /E/ = 4.7(1), g(x) = 1.95(5), g(y) = 2.00(5), and g(z) = 2.11(5). This magnitude of the zero-field splitting ( approximately 840 GHz) is too large for successful detection of resonances, even for current HFEPR spectrometers. The electronic structure of these complexes is discussed in terms of their molecular structure and previous electronic absorption spectroscopic studies. This analysis, which involved fitting of experimental data to ligand-field parameters, shows that the halo ligands act as strong pi-donors, while the triphenylphosphane ligands are pi-acceptors.

Electron Spin Resonance Spectroscopy↗