Discrimination of mononuclear and dinuclear dinitrosyl iron complexes (DNICs) by S K-edge X-ray absorption spectroscopy: insight into the electronic structure and reactivity of DNICs

In addition to probing the formation of dinitrosyl iron complexes (DNICs) by the characteristic Fe K-edge pre-edge absorption energy ranging from 7113.4 to 7113.8 eV, the distinct S K-edge pre-edge absorption energy and pattern can serve as an efficient tool to unambiguously characterize and discriminate mononuclear DNICs and dinuclear DNICs containing bridged-thiolate and bridged-sulfide ligands. The higher Fe-S bond covalency modulated by the stronger electron-donating thiolates promotes the Fe → NO π-electron back-donation to strengthen the Fe-NO bond and weaken the NO-release ability of the mononuclear DNICs, which is supported by the Raman ν(Fe-NO) stretching frequency. The Fe-S bond covalency of DNICs further rationalizes the binding preference of the {Fe(NO)(2)} motif toward thiolates following the trend of [SEt](-) > [SPh](-) > [SC(7)H(4)SN](-). The relative d-manifold energy derived from S K-edge XAS as well as the Fe K-edge pre-edge energy reveals that the electronic structure of the {Fe(NO)(2)}(9) core of the mononuclear DNICs [(NO)(2)Fe(SR)(2)](-) is best described as {Fe(III)(NO(-))(2)}(9) compared to [{Fe(III)(NO(-))(2)}(9)-{Fe(III)(NO(-))(2)}(9)] for the dinuclear DNICs [Fe(2)(μ-SEt)(μ-S)(NO)(4)](-) and [Fe(2)(μ-S)(2)(NO)(4)](2-).     

Determination by X-ray absorption spectroscopy of the Fe-Fe separation in the oxidized form of the hydroxylase of methane monooxygenase alone and in the presence of MMOD

The diiron active site in the hydroxylase of Methylococcus capsulatus (Bath) methane monooxygenase (MMOH) has been studied in the oxidized form by X-ray absorption spectroscopy (XAS). Previous investigations by XAS and X-ray crystallography have identified two different distances (3.0 and 3.4 angstroms) between the two Fe atoms in the dinuclear site. The present study has employed a systematic extended X-ray absorption fine structure (EXAFS) fitting methodology, utilizing known and simulated active site and relevant model structures, to determine unambiguously the Fe-Fe separation in the oxidized form of MMOH. Consistent and unique fits were only possible for an Fe-Fe distance of 3.0 angstroms. This methodology was then applied to study potential changes in the active site local structure in the presence of MMOD, a protein of unknown function in multicomponent MMO. Fe K-edge and EXAFS analyses revealed negligible changes in the diiron site electronic and geometric structure upon addition of MMOD to oxidized MMOH.     

Picosecond X-ray absorption spectroscopy of a photoinduced iron(II) spin crossover reaction in solution

In this study, we perform steady-state and time-resolved X-ray absorption spectroscopy (XAS) on the iron K-edge of [Fe(tren(py)3)](PF6)2 dissolved in acetonitrile solution. Static XAS measurements on the low-spin parent compound and its high-spin analogue, [Fe(tren(6-Me-py)3)](PF6)2, reveal distinct spectroscopic signatures for the two spin states in the X-ray absorption near-edge structure (XANES) and in the X-ray absorption fine structure (EXAFS). For the time-resolved studies, 100 fs, 400 nm pump pulses initiate a charge-transfer transition in the low-spin complex. The subsequent electronic and geometric changes associated with the formation of the high-spin excited state are probed with 70 ps, 7.1 keV, tunable X-ray pulses derived from the Advanced Light Source (ALS). Modeling of the transient XAS data reveals that the average iron-nitrogen (Fe-N) bond is lengthened by 0.21+/-0.03 A in the high-spin excited state relative to the ground state within 70 ps. This structural modification causes a change in the metal-ligand interactions as reflected by the altered density of states of the unoccupied metal orbitals. Our results constitute the first direct measurements of the dynamic atomic and electronic structural rearrangements occurring during a photoinduced FeII spin crossover reaction in solution via picosecond X-ray absorption spectroscopy.     

Characterization of Sol-Gel-synthesized LiFePO4 by multiple scattering XAFS

X-ray absorption spectroscopy (XAS) was used to investigate the local structure arrangements of submicrocrystalline lithium iron phosphate and its precursors. The former material, proven to be very promising as active cathode material in lithium metal and lithium-ion batteries, was synthesized through a new procedure that combines a simple sol-gel precipitation with a moderate temperature (e.g., low cost) heat treatment. X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra taken at the Fe K-edge pointed out the modification of the Fe site during the synthesis steps that allow one to produce the submicrometer size crystalline LiFePO4 (active material) useful for batteries applications. The XAS investigation has shown that such a material is different from the conventional crystalline LiFePO4 on the short-range order. The difference is attributed to the synthesis procedure.     

X-ray absorption spectroscopic investigation of the spin-transition character in a series of single-site perturbed iron(II) complexes

Select ferrous spin-transition complexes with the pentadentate ligand 2,6-bis(bis(2-pyridyl)methoxymethane)pyridine (PY5) were examined using variable-temperature solution solid-state magnetic susceptibility, crystallography, X-ray absorption spectroscopy (XAS), and UV/vis absorption spectroscopy. Altering the single exogeneous ligand, X, of [Fe(PY5)(X)]n)+ is sufficient to change the spin-state of the complexes. When X is the weak-field ligand Cl-, the resultant Fe complex is high-spin from 4 to 300 K, whereas the stronger-field ligand MeCN generates a low-spin complex over this temperature range. With intermediate-strength exogenous ligands (X = N3-, MeOH), the complexes undergo a spin-transition. [Fe(PY5)(N3)]+, as a crystalline solid, transitions gradually from a high-spin to a low-spin complex as the temperature is decreased, as evidenced by X-ray crystallography and solid-state magnetic susceptibility measurements. The spin-transition is also evident from changes in the pre-edge and EXAFS regions of the XAS Fe K-edge spectra on a ground crystalline sample. The spin-transition observed with [Fe(PY5)(MeOH)]2+ appears abrupt by solid-state magnetic susceptibility measurements, but gradual by XAS analysis, differences attributed to sample preparation. This research highlights the strengths of XAS in determining the electronic and geometric structure of such spin-transition complexes and underscores the importance of identical sample preparation in the investigation of these physical properties.     

Changes in electronic structure upon lithium insertion into Fe2(SO4)3 and Fe2(MoO4)3 investigated by X-ray absorption spectroscopy

Changes in electronic structure upon electrochemical lithium insertion into two iron compounds, namely, rhombohedral Fe2(SO4)3 with a NASICON-type structure and monoclinic Fe2(MoO4)3, were investigated using X-ray absorption spectroscopy (XAS). Fe K-edge and L(III)- and L(II)-edge XAS revealed that the rearrangement of Fe d electrons or rehybridization of Fe d-O p bonding took place accompanied by the reduction of Fe ions upon Li insertion for both samples and that a larger change in spectra was observed in Fe2(SO4)3. In addition, the changes in the electronic structure of the polyanion units XO4(2-) (X = S or Mo) after Li insertion were also investigated by O K-edge and S K-edge or Mo L(III)-edge XAS. The results indicated that the electronic structure around oxygen markedly changed in Fe2(MoO4)3, while no significant change was observed in Fe2(SO4)3.     

In situ Fe K-edge X-ray absorption fine structure of a nitrosyl adduct of iron phthalocyanine irreversibly adsorbed on a high area carbon electrode in an acidic electrolyte

Key aspects of the microenvironment surrounding the Fe center in the nitrosyl adduct of iron phthalocyanine, [Fe(Pc)(NO)], have been elucidated from the analysis of the Fe K-edge extended X-ray absorption fine structure (EXAFS) of the material adsorbed on the surface of a high area carbon electrode recorded in situ, in 0.5 M H(2)SO(4). Statistical best fits to the EXAFS data place the Fe center in a five-coordinated square pyramidal configuration shifted away from the Pc plane toward the axially bound NO bent at an angle of ca. 40 degrees with respect to the normal to the Pc plane. This environment is analogous to that of Fe in the nitrosyl adduct of crystalline [Fe(TPP)], where TPP = meso-tetraphenylporphyrinato(2-), determined from X-ray diffraction.     

Solution [Cu(amm)]2+ is a strongly solvated square pyramid: a full account of the copper K-edge XAS spectrum within single-electron theory

The solution structure of Cu(II) in 4 M aqueous ammonia, [Cu(amm)](2+), was assessed using copper K-edge extended X-ray absorption fine structure (EXAFS) and Minuit XANes (MXAN) analyses. Tested structures included trigonal planar, planar and D2d -tetragonal, regular and distorted square pyramids, trigonal bipyramids, and Jahn-Teller distorted octahedra. Each approach converged to the same axially elongated square pyramid, 4 x Cu-Neq=2.00+/-0.02 A and 1 x Cu-Nax=2.16+/-0.02 A (EXAFS) or 2.20+/-0.07 A (MXAN), with strongly localized solvation shells. In the MXAN model, four equatorial ammonias averaged 13 degrees below the Cu(II) xy-plane, which was 0.45+/-0.1 A above the mean N4 plane. When the axial ligand equilibrium partial occupancies of about 0.65 ammonia and 0.35 water were included, EXAFS modeling found Cu-Lax distances of 2.16 and 2.31 A, respectively, reproducing the distances found in the crystal structures of [Cu(NH3)5](2+) and [Cu(NH3)4(H2O)](2+). A transverse axially localized solvent molecule was found at 2.8 A (EXAFS) or 3.1 A (MXAN). Six second-shell solvent molecules were also found at about 3.4+/-0.01 (EXAFS) or 3.8+/-0.2 A (MXAN). The structure of Cu(II) in 4 M pH 10 aqueous NH 3 may be notationally described as {[Cu(NH 3)4.62(H2O)0.38](solv)}(2+).6solv, solv=H2O, NH 3. The prominent shoulder and duplexed maximum of the rising K-edge XAS of [Cu(amm)](2+) primarily reflect the durable and well-organized solvation shells, not found around [Cu(H2O)5](2+), rather than two-electron shakedown transitions. Not accounting for solvent scattering thus may confound XAS-based estimates of metal-ligand covalency. [Cu(amm)](2+) continues the dissymmetry previously found for the solution structure of [Cu(H2O)5](2+), again contradicting the rack-bonding theory of blue copper proteins.     

Investigation of the charge compensation mechanism on the electrochemically Li-ion deintercalated Li1-xCo1/3Ni1/3Mn1/3O2 electrode system by combination of soft and hard X-ray absorption spectroscopy

In situ hard X-ray absorption spectroscopy (XAS) at metal K-edges and soft XAS at O K-edge and metal L-edges have been carried out during the first charging process for the layered Li1-xCo1/3Ni1/3Mn1/3O2 cathode material. The metal K-edge XANES results show that the major charge compensation at the metal site during Li-ion deintercalation is achieved by the oxidation of Ni2+ ions, while the manganese ions and the cobalt ions remain mostly unchanged in the Mn4+ and Co3+ state. These conclusions are in good agreement with the results of the metal K-edge EXAFS data. Metal L-edge XAS results at different charge states in both the FY and PEY modes show that, unlike Mn and Co ions, Ni ions at the surface are oxidized to Ni3+ during charge, whereas Ni ions in the bulk are further oxidized to Ni4+ during charge. From the observation of O K-edge XAS results, we can conclude that a large portion of the charge compensation during Li-ion deintercalation is achieved in the oxygen site. By comparison to our earlier results on the Li1-xNi0.5Mn0.5O2 system, we attribute the active participation of oxygen in the redox process in Li1-xCo1/3Ni1/3Mn1/3O2 to be related to the presence of Co in this system.     

Sulfur K-edge XAS and DFT calculations on nitrile hydratase: geometric and electronic structure of the non-heme iron active site

The geometric and electronic structure of the active site of the non-heme iron enzyme nitrile hydratase (NHase) is studied using sulfur K-edge XAS and DFT calculations. Using thiolate (RS(-))-, sulfenate (RSO(-))-, and sulfinate (RSO(2)(-))-ligated model complexes to provide benchmark spectral parameters, the results show that the S K-edge XAS is sensitive to the oxidation state of S-containing ligands and that the spectrum of the RSO(-) species changes upon protonation as the S-O bond is elongated (by approximately 0.1 A). These signature features are used to identify the three cysteine residues coordinated to the low-spin Fe(III) in the active site of NHase as CysS(-), CysSOH, and CysSO(2)(-) both in the NO-bound inactive form and in the photolyzed active form. These results are correlated to geometry-optimized DFT calculations. The pre-edge region of the X-ray absorption spectrum is sensitive to the Z(eff) of the Fe and reveals that the Fe in [FeNO](6) NHase species has a Z(eff) very similar to that of its photolyzed Fe(III) counterpart. DFT calculations reveal that this results from the strong pi back-bonding into the pi antibonding orbital of NO, which shifts significant charge from the formally t(2)(6) low-spin metal to the coordinated NO.     

Structure of iron and manganese ions substituted in the framework of nanoporous AlPO-5 material

The structure of iron and managanese ions substituted in the framework of nanoporous AlPO-5 is determined by ex situ and in situ X-ray absorption spectroscopy. Fe K-edge XANES and EXAFS studies clearly indicate that iron ions are present as Fe(III) in octahedral coordination in the assynthesised material and tetrahedral coordination in the calcined material in both pure FeAlPO-5 and FeMnalPO-5. XANES and EXAFS results also indicate that reaction with hydrogen peroxide causes the removal of Fe(III) ions from the framework. Mn K-edge XANES and EXAFS of FeMnAlPO-5 samples indicate that Mn(II) ions are present in the framework, tetrahedrally coordinated, in the as-synthesised material but upon calcination it is found that the Mn(II) ions are removed from the framework, suggesting a different synthesis strategy is necessary to stabilise the Mn(II) ions in the framework simultaneously with Fe(III) ions.     

Defining chemical species in complex environments using K-edge X-ray absorption spectroscopy: vanadium in intact blood cells and Henze solution from the tunicate Ascidia ceratodes

A K-edge X-ray absorption spectrum (XAS) fitting approach has been developed to speciate elements of interest in complex materials and used here to model the storage of biological vanadium within whole blood cells from the tunicate Ascidia ceratodes. The response of the K-edge XAS of solution-phase V(III) to increasing c(sulfate) at constant pH 1.8 produced specific and systematic effects in the preedge transition at 5468.8 eV (preedge transitions: 1s-->4A2 at 5464.9 +/- 0.1 eV, 1s-->4T2 at 5466.9 +/- 0.1 eV, and 1s-->4T1 at 5468.8 +/- 0.1 eV for 11 different V(III)/sulfate solutions). In contrast, variations in acidity (as pH) at constant c(sulfate) systematically modified the V(III) preedge XAS at 5466.9 eV. The energy position of the K-edge absorption maximum also serially shifted -0.32 eV/pH unit, from 5483.7 eV (pH 3.0) to 5484.7 eV (pH 0.3). Fits to the V-K XAS of two samples of A. ceratodes whole blood cells representing dozens of animals implied storage of V(III) ions in four predominant solution regimes: approximately 10% high sulfate/pH 0 acid; approximately 40% high sulfate/pH 1.8 acid; approximately 40% moderate sulfate/pH 1.8 acid; approximately 10% moderate sulfate/pH 3 acid. For lysed blood cells, the best fit represented 63% of the V(III) in a pH 1.6 sulfate-free environment and a further 16% in acidic sulfate solution. Nearly 18% of lysed cells vanadium(III) appeared in a tris(catecholate)-like environment. A detailed speciation of biological vanadium complex ions was calculated from these fits by application of the known equilibrium constants governing V(III) and sulfate in acidic aqueous solution. The utility of blood cell V(III) to ascidians is discussed. Fits to K-edge XAS spectra using the XAS spectra of appropriate models are suggested to be generally applicable to elucidating the state of metal ions in a wide variety of complex environments.     

Structural insights into nonheme alkylperoxoiron(III) and oxoiron(IV) intermediates by X-ray absorption spectroscopy

Transient mononuclear low-spin alkylperoxoiron(III) and oxoiron(IV) complexes that are relevant to the activation of dioxygen by nonheme iron enzymes have been generated from synthetic iron(II) complexes of neutral tetradentate (TPA) and pentadentate (N4Py, Bn-TPEN) ligands and structurally characterized by means of Fe K-edge X-ray absorption spectroscopy (XAS). Notable features obtained from fits of the EXAFS region are Fe-O bond lengths of 1.78 A for the alkylperoxoiron(III) intermediates and 1.65-1.68 A for the oxoiron(IV) intermediates, reflecting different strengths in the Fe-O pi interactions. These differences are also observed in the intensities of the 1s-to-3d transitions in the XANES region, which increase from 4 units for the nearly octahedral iron(II) precursor to 9-15 units for the alkylperoxoiron(III) intermediates to 25-29 units for the oxoiron(IV) species.     

Electronic and local structural changes in Li(2+x)Ti3O7 ramsdellite compounds upon electrochemical Li-ion insertion reactions by X-ray absorption spectroscopy

Electronic and local structural changes in ramsdellite-type Li(2+x)Ti3O7 compound were investigated by X-ray absorption spectroscopy (XAS) measurements. Upon electrochemical Li-ion insertions, the host lattice with ramsdellite structure is retained, indicated by X-ray powder diffraction. Ti K-edge extended X-ray absorption fine structure (EXAFS) analysis shows, however, slight local structural distortions around Ti ions. The energy shifts and the changes in the peak intensity of Ti K-edge and Ti L-edge XAS reveal the reducing oxidation states of Ti ions as the amount of electrochemically-inserted Li-ion increases. Equally important, oxide ions have a significant effect on the electronic transfer process, suggested by O K-edge XAS. These results on electronic structural changes were interpreted using the Zaanen-Sawatzky-Allen scheme.     

Synthesis and characterization of high nuclearity iron(III) phosphonate molecular clusters

Three new phosphonic acid ligands (4- (t)butylphenyl phosphonic acid, 3,5-dimethylphenyl phosphonic acid, and diphenylmethylphosphonic acid) have been synthesized and employed in search of high molecularity iron(III) clusters. The cluster compounds are characterized by single crystal X-ray diffraction and magnetic measurements. The solvothermal reaction of FeCl 3.6H 2O with diphenylacetic acid and p- (t)butylphenyl phosphonic acid resulted in an unprecedented dodecanuclear cluster [Fe 12(mu 2-O) 4(mu 3-O) 4(O 2CCHPh 2) 14(4- (t)buPhPO 3H) 6]( 1) having a double butterfly like core structure. [Fe 12(mu 2-O) 4(mu 3-O) 4(O 2CPh) 14(C 10H 17PO 3H) 6]( 2), another dodecanuclear cluster having core structure similar to 1, has been synthesized in a reaction between [Fe 3O(O 2CPh) 6(H 2O) 3]Cl and camphylphosphonic acid in the presence of triethylamine at ambient condition. 3,5-Dimethylphenyl phosphonic acid on reacting solvothermally with an oxo-centered iron triangle [Fe 3O(O 2CCMe 3) 6(H 2O) 3]Cl gives a nonanuclear cluster [Fe 9(mu 3-O) 4(O 3PPh(Me) 2) 3(O 2CCMe 3) 13]( 3) having icosahedral type core structure where three positions of the iron atoms have been replaced by phosphorus. Another nonanuclear [Fe 9(O) 3(OH) 3(O 3PCHPh 2) 6(O 2CCMe 3) 6(H 2O) 9] ( 4), having a distorted cylindrical core structure, has been synthesized in a similar solvothermal reaction between [Fe 3O(O 2CCMe 3) 6(H 2O) 3]Cl and biphenylmethyl phosphonic acid. All compounds are characterized by IR spectra, elemental analysis, as well as single crystal X-ray analysis. Magnetic measurements for all the compounds reveal that there are antiferromagnetic interactions between the metal centers.     

Simulating picosecond iron K-edge X-ray absorption spectra by ab initio methods to study photoinduced changes in the electronic structure of Fe(II) spin crossover complexes

Recent time-resolved X-ray absorption experiments probing the low-spin to high-spin photoconversion in Fe(II) complexes have monitored the complex interplay between electronic and structural degrees of freedom on an ultrafast time scale. In this study, we use transition potential (TP) and time-dependent (TD) DFT to simulate the picosecond time-resolved iron K-edge X-ray absorption spectrum of the spin crossover (SCO) complex, [Fe(tren(py)(3))](2+). This is achieved by simulating the X-ray absorption spectrum of [Fe(tren(py)(3))](2+) in its low-spin (LS), (1)A(1), ground state and its high-spin (HS), (5)T(2), excited state. These results are compared with the X-ray absorption spectrum of the high-spin analogue (HSA), [Fe(tren(6-Me-py)(3))](2+), which has a (5)T(2) ground state. We show that the TP-DFT methodology can simulate a 40 eV range of the iron K-edge XANES spectrum reproducing all of the major features observed in the static and transient spectra of the LS, HS, and HSA complexes. The pre-edge region of the K-edge spectrum, simulated by TD-DFT, is shown to be highly sensitive to metal-ligand bonding. Changes in the intensity of the pre-edge region are shown to be sensitive to both symmetry and π-backbonding by analysis of relative electric dipole and quadrupole contributions to the transition moments. We generate a spectroscopic map of the iron 3d orbitals from our TD-DFT results and determine ligand field splitting energies of 1.55 and 1.35 eV for the HS and HSA complexes, respectively. We investigate the use of different functionals finding that hybrid functionals (such as PBE0) produce the best results. Finally, we provide a detailed comparison of our results with theoretical methods that have been previously used to interpret Fe K-edge spectroscopy of equilibrium and time-resolved SCO complexes.     

Quantitative adsorption and local structures of gallium(III) at the water-alpha-FeOOH interface

The adsorption of Ga(III) at the water-alpha-FeOOH (goethite) interface has been investigated by means of quantitative adsorption experiments, extended X-ray absorption fine structure (EXAFS) spectroscopy, and surface complexation modeling. Under the conditions studied, pH range 3-11 and surface coverages of 0.9-3.2 micromol/m2, Ga(III) was found to adsorb strongly to alpha-FeOOH, and the surface species were more resistant toward hydrolysis and formation of soluble Ga(OH)4- than either solid gallium hydroxides or soluble polynuclear complexes. The EXAFS measurements revealed the presence of octahedral Ga(III) complexes at the water-alpha-FeOOH interface, with practically no structural variations as a function of pH or total gallium concentration. Analysis of the first coordination shell required an anharmonic model indicating a distorted geometry of the GaO6 octahedra, with mean Ga-O distances at 1.96-1.98 angstroms. A method based on the continuous Cauchy wavelet transforms (CCWT) was used to identify backscattering atoms in the higher coordination shells. This analysis indicated predominately Fe backscattering, and the quantitative data fitting resulted in three Ga-Fe paths at 3.05, 3.2, and 3.55 angstroms, which correspond to two edge-sharing and one corner-sharing linkage, respectively. The collective results from EXAFS spectroscopy showed that Ga(III) adsorbs to Fe equivalent sites at the surface alpha-FeOOH as an extension of the rows of Fe octahedra in the bulk structure. This interpretation was further corroborated by a Ga-Fe-Fe multiple scattering path at 6.13 angstroms. The quantitative adsorption and proton data were modeled using a surface complexation formalism based on a 1 pK(a) constant capacitance model. In agreement with the EXAFS results, the model obtained included one predominating surface complex with the stoichiometry [triple bond]FeOGa(OH)2(-0.5) and the stability constant log beta(intr.) = -2.55 +/- 0.04 ([triple bond]FeOH(-0.5) + Ga3+ + 2H2O <--> [triple bond]FeOGa(OH)2(-0.5) + 3H+).     

1s2p resonant inelastic X-ray scattering of iron oxides

1s2p resonant inelastic X-ray scattering (RIXS) spectroscopy has been measured for a series of iron oxides, including octahedral and tetrahedral Fe(II) and Fe(III) systems. Their spectral shapes have been analyzed and explained using crystal-field multiplet simulations. The RIXS planes and the K-edge and L-edge X-ray absorption spectra related to these RIXS planes will be discussed with respect to their analytical opportunities. It is concluded that the full power and possibilities of 1s2p RIXS needs an overall resolution of 0.3 eV. This will yield a technique with more detailed information than K-edge and L-edge X-ray absorption combined, obtained in a single experiment. Another major advantage is that 1s2p RIXS involves only hard X-rays, and experiments under essentially any condition and on any system are feasible.     

Cooperative ligation,back-bonding,and possible pyridine-pyridine interactions in tetrapyridine-vanadium(II): a visible and X-ray spectroscopic study

The binding of pyridine by V(II) in aqueous solution shows evidence for the late onset of cooperativity. The K(1) governing formation of [V(py)](2+) (lambda(max) = 404 nm, epsilon(max) = 1.43 +/- 0.3 M(-1) cm(-1)) was determined spectrophotometrically to be 11.0 +/- 0.3 M(-)(1), while K(1) for isonicotinamide was found to be 5.0 +/- 0.1 M(-1). These values are in the low range for 3d M(2+) ions and indicate that V(II).py back-bonding is not significant in the formation of the 1:1 complex. Titration of 10.5 mM V(II) with pyridine in aqueous solution showed an absorption plateau at about 1 M added pyridine, indicating a reaction terminus. Vanadium K-edge EXAFS analysis of 63 mM V(II) in 2 M pyridine solution revealed six first-shell N/O ligands at 2.14 A and 4 +/- 1 pyridine ligands per V(II). UV/vis absorption spectroscopy indicated that the same terminal V(II) species was present in both experiments. Model calculations showed that in the absence of back-bonding only 2.0 +/- 0.2 and 2.4 +/- 0.2 pyridine ligands would be present, respectively. Cooperativity in multistage binding of pyridine by [V(aq)](2+) is thus indicated. XAS K-edge spectroscopy of crystalline [V(O(3)SCF(3))(2)(py)(4)] and of V(II) in 2 M pyridine solution each exhibited the analogous 1s --> (5)E(g) and 1s --> (5)T(2g) transitions, at 5465.5 and 5467.5 eV, and 5465.2 and 5467.4 eV, respectively, consistent with the EXAFS analysis. In contrast, [V(py)(6)](PF(6))(2) and [V(H(2)O)(6)]SO(4) show four 1s --> 3d XAS transitions suggestive of a Jahn-Teller distorted excited state. Comparison of the M(II)[bond]N(py) bond lengths in V(II) and Fe(II) tetrapyridines shows that the V(II)[bond]N(py) distances are about 0.06 A shorter than predicted from ionic radii. For [VX(2)(R-py)(4)] (X = Cl(-), CF(3)SO(3)(-); R = 4-Et, H, 3-EtOOC), the E(1/2) values of the V(II)/V(III) couples correlate linearly with the Hammett sigma values of the R group. These findings indicate that pi back-bonding is important in [V(py)(4)](2+) even though absent in [V(py)](2+). The paramagnetism of [V(O(3)SCF(3))(2)(py)(4)] in CHCl(3), 3.8 +/- 0.2 mu(B), revealed that the onset of back-bonding is not accompanied by a spin change. Analysis of the geometries of V(II) and Fe(II) tetrapyridines indicates that the ubiquitous propeller motif accompanying tetrapyridine ligation may be due to eight dipole interactions arising from the juxtaposed C-H edges and pi clouds of adjoining ligands, worth about -6 kJ each. However, this is not the source of the cooperativity in the binding of multiple pyridines by V(II) because the same interactions are present in the Fe(II)-tetrapyridines, which do not show cooperative ligand binding. Cooperativity in the binding of pyridine by V(II) is then assigned by default to V(II)-pyridine back-bonding, which emerges only after the first pyridine is bound.