Investigating the structural and electronic properties of nitrile hydratase model iron(III) complexes using projected unrestricted Hartree-Fock (PUHF) calculations

Important structural and mechanistic details concerning the non-heme, low-spin Fe(III) center in nitrile hydratase (NHase) remain poorly understood. We now report projection unrestricted Hartree-Fock (PUHF) calculations on the spin preferences of a series of inorganic complexes in which Fe(III) is coordinated by a mixed set of N/S ligands. Given that many of these compounds have been prepared as models of the NHase metal center, this study has allowed us to evaluate this computational approach as a tool for future calculations on the electronic structure of the NHase Fe(III) center itself. When used in combination with the INDO/S semiempirical model, the PUHF method correctly predicts the experimentally observed spin state for 12 of the 13 Fe(III)-containing complexes studied here. The one compound for which there is disagreement between our theoretical calculations and experimental observation exhibits temperature-dependent spin behavior. In this case, the failure of the PUHF-INDO/S approach may be associated with differences between the structure of the Fe(III) complex present under the conditions used to measure the spin preference and that observed by X-ray crystallography. A preliminary analysis of the role of the N/S ligands and coordination geometry in defining the Fe(III) spin preferences in these complexes has also been undertaken by computing the electronic properties of the lowest energy Fe(III) spin states. While any detailed interpretation of our results is constrained both by the limited set of well-characterized Fe(III) complexes used in this study and by the complicated dependence of Fe(III) spin preference upon metal-ligand interactions and coordination geometry, these PUHF-INDO/S calculations support the hypothesis that the deprotonated amide nitrogens coordinating the metal stabilize the low-spin Fe(III) ground state seen in NHase. Strong evidence that the sulfur ligands exclusively define the Fe(III) spin state preference by forming metal-ligand bonds with significant covalent character is not provided by these computational studies. This might, however, reflect limitations in modeling these systems at the INDO/S level of theory.     

Theoretical, spectroscopic, and mechanistic studies on transition-metal dinitrogen complexes: implications to reactivity and relevance to the nitrogenase problem

Dinitrogen complexes of transition metals exhibit different binding geometries of N2 (end-on terminal, end-on bridging, side-on bridging, side-on end-on bridging), which are investigated by spectroscopy and DFT calculations, analyzing their electronic structure and reactivity. For comparison, a bis(mu-nitrido) complex, where the N--N bond has been split, has been studied as well. Most of these systems are highly covalent, and have strong metal-nitrogen bonds. In the present review, particular emphasis is put on a consideration of the activation of the coordinated dinitrogen ligand, making it susceptible to protonation, reactions with electrophiles or cleavage. In this context, theoretical, structural, and spectroscopic data giving informations on the amount of charge on the N2 unit are presented. The orbital interactions leading to a charge transfer from the metals to the dinitrogen ligand and the charge distribution within the coordinated N2 group are analyzed. Correlations between the binding mode and the observed reactivity of N2 are discussed.     

Comparison of side-on and end-on coordination of E2 ligands in complexes [W(CO)5E2] (E=N,P, As,Sb, Bi,Si-, Ge-, Sn-, Pb-)

Complexes of W(CO)(5) with neutral diatomic pnictogen ligands N(2), P(2), As(2), Sb(2), and Bi(2) and anionic Group 14 ligands Si(2) (2-), Ge(2) (2-), Sn(2) (2-), and Pb(2) (2-) coordinated in both side-on and end-on fashion have been optimized by using density functional theory at the BP86 level with valence sets of TZP quality. The calculated bond energies have been used to compare the preferential binding modes of each respective ligand. The results were interpreted by analyzing the nature of the interaction between the ligands and the metal fragment using an energy partitioning method. This yields quantitative information regarding the strength of covalent and electrostatic interactions between the metal and ligand, as well as the contributions by orbitals of different symmetry to the covalent bonding. Results show that all the ligands studied bind preferentially in a side-on coordination mode, with the exception of N(2), which prefers to coordinate in an end-on mode. The preference of the heavier homologues P(2)-Bi(2) for binding in a side-on mode over the end-on mode in the neutral complexes [(CO)(5)WE(2)] comes mainly from the much stronger electrostatic attraction in the former species. The energy difference between the side-on and end-on isomers of the negatively charged complexes with the ligands Si(2) (2-), Ge(2) (2-), Sn(2) (2-), and Pb(2) (2-) is much less and it cannot be ascribed to a particular bonding component.     

Crystal structures of thermoelectric n- and p-type Ba8Ga16Ge30 studied by single crystal, multitemperature, neutron diffraction, conventional X-ray diffraction and resonant synchrotron X-ray diffraction

Comprehensive single-crystal structural investigations of n- and p-type Ba8Ga16Ge30 have been carried out using multitemperature neutron and conventional X-ray diffraction as well as resonant synchrotron X-ray diffraction. The data show that the guest atom positions and dynamics are very similar in the two structures, although the barium atoms are slightly more displaced from the cage centers in the p-type structure than in the n-type structure (Deltad = 0.025 A). For both structures Fourier difference maps calculated from very high-resolution neutron diffraction data (sin theta/lambda > 2 A-1) show that the Ba nuclear density at lowest temperatures (15 K) is distributed in a torus around the crystallographic 6d site with maxima in the 24j positions. At room temperature the maxima have shifted to the 24k position. Analysis of atomic displacement parameters give Einstein temperatures of approximately 60(1) K for both structures. Thus, the fundamental difference in the low temperature thermal conductivity observed for p- and n-type Ba8Ga16Ge30 appear not to be directly related to the guest atom behavior as is commonly assumed in thermoelectric research. The neutron data and the resonant synchrotron X-ray data facilitate refinement of Ga/Ge framework occupancies. The Ga atoms have a clear preference for the 6c site with the preference being somewhat stronger for the n-type structure.     

Stereoelectronic effects on molecular geometries and state-energy splittings of ligated monocopper dioxygen complexes

The relative energies of side-on versus end-on binding of molecular oxygen to a supported Cu(I) species, and the singlet versus triplet nature of the ground electronic state, are sensitive to the nature of the supporting ligands and, in particular, depend upon their geometric arrangement relative to the O2 binding site. Highly correlated ab initio and density functional theory electronic structure calculations demonstrate that optimal overlap (and oxidative charge transfer) occurs for the side-on geometry, and this is promoted by ligands that raise the energy, thereby enhancing resonance, of the filled Cu dxz orbital that hybridizes with the in-plane pi* orbital of O2. Conversely, ligands that raise the energy of the filled Cu dz2 orbital foster a preference for end-on binding as this is the only mode that permits good overlap with the in-plane O2 pi*. Because the overlap of Cu dz2 with O2 pi* is reduced as compared to the overlap of Cu dxz with the same O2 orbital, the resonance is also reduced, leading to generally more stable triplet states relative to singlets in the end-on geometry as compared to the side-on geometry, where singlet ground states become more easily accessible once ligands are stronger donors. Biradical Cu(II)-O2 superoxide character in the electronic structure of the supported complexes leads to significant challenges for accurate quantum chemical calculations that are best addressed by exploiting the spin-purified M06L local density functional, single-reference completely renormalized coupled-cluster theory, or multireference second-order perturbation theory, all of which provide predictions that are qualitatively and quantitatively consistent with one another.     

Infrared spectroscopy of physisorbed and chemisorbed N2 in the Pt(111)(3x3)N2 structure

Using infrared spectroscopy and low electron energy diffraction, we have investigated the adsorption of N(2), at 30 K, on the Pt(111) and the Pt(111)(1x1)H surfaces. At monolayer coverage, N(2) orders in commensurate (3x3) structures on both surfaces, and we propose that the unit cells contain four molecules in each case. The infrared spectra reveal that N(2) exclusively physisorbs on the Pt(111)(1x1)H surface, while both physisorbed and chemisorbed N(2) is detected on the Pt(111) surface. Physisorbed N(2) is the majority species in the latter case, and the two adsorption states show an almost identical uptake behavior, which indicates that they are intrinsic constituents of the growing (3x3) N(2) islands. An analysis of the infrared absorbance data, based on a simple scaling concept suggested by density functional theory calculations, supports a model in which the (3x3) unit cell contains one chemisorbed molecule in end-on atop configuration and three physisorbed molecules. We note that a classic "pinwheel" structure on a hexagonal lattice, with the end-on chemisorbed N(2) molecules acting as "pins," is compatible with this composition.     

Oxygen isotope effects upon reversible O2-binding reactions: Characterizing mononuclear superoxide and peroxide structures

Identifying intermediates in catalytic oxidation reactions requires the development of new probes of structure and mechanism. Reported here are proof-of-concept studies of oxygen (18O) isotope effects upon reversible O2-binding reactions of classic inorganic compounds. It is shown that the 18O equilibrium isotope effects may be used to differentiate structures where O2 is bound as a side-on peroxide ligand versus an end-on superoxide ligand. The application of 18O equilibrium isotope effects to the interpretation of 18O kinetic isotope effects and the study of O2 activation mechanisms is also discussed.     

Dinitrogen functionalization with bis(cyclopentadienyl) complexes of zirconium and hafnium

The rich chemistry of substituted bis(cyclopentadienyl)zirconium and hafnium complexes bearing side-on coordinated dinitrogen ligands is highlighted in this Perspective. Our studies in this area were initially motivated by the desire to understand side-on vs. end-on dinitrogen coordination in bimetallic zirconocene and hafnocene N2 compounds. In the cases where eta2,eta2-dinitrogen compounds were isolated, both structural and computational data have established significant imido character in the metal-nitrogen bonds. This additional bonding interaction, which is diminished in end-on complexes bearing both terminal and bridging N2 ligands, facilitates dinitrogen functionalization by non-polar reagents including dihydrogen, carbon-hydrogen bonds and weak Br?nsted acids such as water and ethanol. In hafnocene chemistry, where unwanted side-on, end-on isomerization is suppressed, cycloaddition of phenylisocyanate to coordinated N2 has also been accomplished. For N-H bond forming reactions involving H2, kinetic measurements, in addition to isotopic labelling and computational studies, are consistent with dinitrogen functionalization by 1,2-addition involving a highly ordered, four-centred transition structure.     

Can an ancillary ligand lead to a thermodynamically stable end-on 1 : 1 Cu-O2 adduct supported by a beta-diketiminate ligand?

The finding that dioxygen binds end-on to the Cu(B) site in the crystal structure of a precatalytic complex of peptidylglycine alpha-hydroxylating monooxygenase has spurred the search for biomimetic model complexes exhibiting the same dioxygen coordination. Recent work has not only indicated that sterically hindered beta-diketiminate ligands (L(1)) could support side-on 1 : 1 Cu-O(2) adducts, but also that an end-on L(1)Cu(THF)O(2) structure occurs as an unstable intermediate in the oxygenation mechanism of the Cu(I) complex. In this work, density functional theory and multireference methods are used to determine the potential of ancillary ligands, X, other than THF to yield thermodynamically stable end-on L(1)CuXO(2) species. A diverse set of ligands X, comprising phosphines, thiophene, cyclic ethers, acetonitrile, para-substituted pyridines, N-heterocyclic carbenes, and ligands bearing hydrogen bond donors, has been considered in order to identify ligand characteristics which energetically favor end-on L(1)CuXO(2) over: a) reversion to the Cu(I) complex and dioxygen, b) isomerization to side-on L(1)CuXO(2), and c) decay to L(1)CuO(2) and X. Ancillary ligands with judiciously chosen degrees and orientation of steric bulk and which bear potential hydrogen bond donors to an end-on bound dioxygen moiety most favor oxygenation of L(1)CuX to yield end-on L(1)CuXO(2). Conversion to the side-on isomer can be deterred through the use of a sufficiently bulky ligand X, such as one that is at least the size of a 5-membered ring. Loss of X to give L(1)CuO(2) can be made prohibitively endergonic by employing ligands X which are highly electron donating and which backbond strongly with and sigma-donate significantly to copper.     

Unified model to predict self-assembly of nonionic surfactants in solution and adsorption on solid or fluid hydrophobic surfaces: effect of molecular structure

We have developed a pseudo-phase model to predict the self-assembly of nonionic surfactants on hydrophobic solid or fluid interfaces and in bulk solution. The uniqueness of this model is that it provides the relationship between molecular structure and self-assembly in solution and on interfaces. This model requires the input of minimal new experimental data. The remaining model parameters may be calculated on the basis of the surfactant molecular structure. The validity of the model has been established by comparing predictions with a wide array of experimental data for nonionic surfactant adsorption at the hydrophobic solid-water interface and at the air-water interface. The same model is then used to predict the self-assembly in bulk solution. The model predictions for critical aggregation concentration, aggregate shapes, and adsorption isotherms of various surfactants are in good agreement with the experimental data available in the literature.     

Orientation of irreversible adhesion of spherical particles on prolate spheroidal collectors

When one sphere adheres to a second sphere, the location or orientation of the adhesion on the second sphere is seldom considered. However, when a sphere adheres to a prolate spheroid, the orientation of the adhesion is sometimes critical. We have performed Brownian dynamics simulations to predict the orientation of adhesion of a sphere on a prolate spheroid. When the spheroid has a high rotational diffusion coefficient, simulations show that the spherical particle adheres near the end of the spheroid. We tested our model experimentally for two systems: (1) oppositely-charged spherical and spheroidal colloids and (2) like-charged colloidal spheres and E. coli K-12 D21 bacteria. For the latter case, the spheres have previously been shown to adhere only to one end of the bacterium. Experiments in case (1) support the results of the simulations, while data from case (2) do not agree with predictions. Case (2) data reveal that the end-on adhesion of the spheres on the bacteria is not a purely Brownian phenomenon.     

Multi-competitive interaction of As(III) and As(V) oxyanions with Ca(2+), Mg(2+), PO(3-)(4), and CO(2-)(3) ions on goethite

Complex systems, simulating natural conditions like in groundwater, have rarely been studied, since measuring and in particular, modeling of such systems is very challenging. In this paper, the adsorption of the oxyanions of As(III) and As(V) on goethite has been studied in presence of various inorganic macro-elements (Mg(2+), Ca(2+), PO(3-)(4), CO(2-)(3)). We have used 'single-,' 'dual-,' and 'triple-ion' systems. The presence of Ca(2+) and Mg(2+) has no significant effect on As(III) oxyanion (arsenite) adsorption in the pH range relevant for natural groundwater (pH 5-9). In contrast, both Ca(2+) and Mg(2+) promote the adsorption of PO(3-)(4). A similar (electrostatic) effect is expected for the Ca(2+) and Mg(2+) interaction with As(V) oxyanions (arsenate). Phosphate is a major competitor for arsenate as well as arsenite. Although carbonate may act as competitor for both types of As oxyanions, the presence of significant concentrations of phosphate makes the interaction of (bi)carbonate insignificant. The data have been modeled with the charge distribution (CD) model in combination with the extended Stern model option. In the modeling, independently calculated CD values were used for the oxyanions. The CD values for these complexes have been obtained from a bond valence interpretation of MO/DFT (molecular orbital/density functional theory) optimized geometries. The affinity constants (logK) have been found by calibrating the model on data from 'single-ion' systems. The parameters are used to predict the ion adsorption behavior in the multi-component systems. The thus calibrated model is able to predict successfully the ion concentrations in the mixed 2- and 3-component systems as a function of pH and loading. From a practical perspective, data as well as calculations show the dominance of phosphate in regulating the As concentrations. Arsenite (As(OH)(3)) is often less strongly bound than arsenate (AsO(3-)(4)) but arsenite responses less strongly to changes in the phosphate concentration compared to arsenate, i.e., deltalogc(As(III))/deltalogc(PO(4)) approximately 0.4 and deltalogc(As(V))/deltalogc(PO(4)) approximately 0.9 at pH 7. Therefore, the response of As in a sediment on a change in redox conditions will be variable and will depend on the phosphate concentration level.     

On the unprecedented level of dinitrogen activation in the calix[4]arene complex of Nb(III)

The calix[4]arene niobium(III) complex ([L]Nb-N=N-Nb[L] where [L] = p-tert-butylcalix[4]arene), reported to bind N(2) in a μ(2)-linear dimeric capacity and to activate the N(2) triple bond to 1.39 ?, corresponding to the longest N(2) bond known in the end-on coordination mode, was subjected to a computational investigation involving both density functional and wavefunction based methods to establish the basis for the unprecedented level of activation. Replacement of the calix[4]arene ligand with hydroxide or methoxide ligands reveals that the organic backbone structure of the calix[4]arene ligand exerts negligible electronic influence over the metal centre, serving only to geometrically constrain the coordinating phenoxide groups. A fragment bonding analysis shows that metal-to-dinitrogen π* backbonding is the principal Nb-N interaction, providing a strong electronic basis for analogy with other well-characterised three- and four-coordinate complexes which bind N(2) end-on. While the calculated structure of the metallacalix[4]arene unit is reproduced with high accuracy, as is also the Nb-Nb separation, the calculated equilibrium geometry of the complex under a variety of conditions consistently indicates against a 1.39 ? activation of the N(2) bond. Instead, the calculated N-N distances fall within the range 1.26-1.30 ?, a result concordant with closely related three- and four-coordinate μ(2)-N(2) complexes as well as predictions derived from trends in N-N stretching frequency for a number of crystallographically characterized linear N(2) activators. A number of potential causes for this bond length discrepancy are explored.     

Electronic structure contributions to electron-transfer reactivity in iron-sulfur active sites: 1. Photoelectron spectroscopic determination of electronic relaxation

Electronic relaxation, the change in molecular electronic structure as a response to oxidation, is investigated in [FeX(4)](2)(-)(,1)(-) (X = Cl, SR) model complexes. Photoelectron spectroscopy, in conjunction with density functional methods, is used to define and evaluate the core and valence electronic relaxation upon ionization of [FeX(4)](2)(-). The presence of intense yet formally forbidden charge-transfer satellite peaks in the PES data is a direct reflection of electronic relaxation. The phenomenon is evaluated as a function of charge redistribution at the metal center (Deltaq(rlx)) resulting from changes in the electronic structure. This charge redistribution is calculated from experimental core and valence PES data using a valence bond configuration interaction (VBCI) model. It is found that electronic relaxation is very large for both core (Fe 2p) and valence (Fe 3d) ionization processes and that it is greater in [Fe(SR)(4)](2)(-) than in [FeCl(4)](2)(-). Similar results are obtained from DFT calculations. The results suggest that, although the lowest-energy valence ionization (from the redox-active molecular orbital) is metal-based, electronic relaxation causes a dramatic redistribution of electron density ( approximately 0.7ē) from the ligands to the metal center corresponding to a generalized increase in covalency over all M-L bonds. The more covalent tetrathiolate achieves a larger Deltaq(rlx) because the LMCT states responsible for relaxation are significantly lower in energy than those in the tetrachloride. The large observed electronic relaxation can make significant contributions to the thermodynamics and kinetics of electron transfer in inorganic systems.     

Structure of Protein Layers during Competitive Adsorption

The formation of protein layers during competitive adsorption was studied with ellipsometry. Single, binary, and ternary protein solutions of human serum albumin (HSA), IgG, and fibrinogen (Fgn) were investigated at concentrations corresponding to blood plasma diluted 1/100. As a model surface, hydrophobic hexamethyldisiloxane (HMDSO) plasma polymer modified silica was used. By using multiambient media measurements of the bare substrate prior to protein adsorption the adsorbed amount as well as the thickness and refractive index of the adsorbed protein layer could be followedin situand in real time. Under conditions used in these experiments neither IgG nor fibrinogen could fully displace serum albumin from the interface. The buildup of the protein layer occurred via different mechanisms for the different protein systems. Fgn adsorbed in a rather flat orientation at low adsorbed amounts, while at higher surface coverage the protein reoriented to a more upright orientation in order to accommodate more molecules in the adsorbed layer. IgG adsorption proceeded mainly end-on with little reorientation or conformational change on adsorption. Finally, for HSA an adsorbed layer thickness greater than the molecular dimensions was observed at high concentrations (although not at low), indicating that aggregates or multilayers formed on HMDSO plasma polymer surfaces. For all protein mixtures the adsorbed layer structure and buildup indicated that Fgn was the protein dominating the adsorbed layer, although HSA partially blocked the adsorption of this protein. At high surface concentration, HSA/Fgn mixtures show an abrupt change in both adsorbed layer thickness and refractive index suggesting, e.g., an interfacial phase transition of the mixed protein layer. A similar but less pronounced behavior was observed for HSA/IgG. For IgG/Fgn and HSA/IgG/Fgn a buildup of the adsorbed layer similar to that displayed by Fgn alone was observed.     

四唑负离子与脒正离子复合物稳定性的理论研究

采用密度泛函B3LYP/6-31+G(d,p) 方法和自洽反应场极化连续模型(PCM)研究四唑负离子与脒类(乙脒或苄脒)正离子形成的两种形式的复合物(末端和侧端)及甲酸根负离子与脒类(乙脒或苄脒)正离子形成的复合物在气相和二甲亚砜（DMSO）溶剂中的稳定性。在气相中,四唑-乙脒和四唑-苄脒复合物的相互作用能(∆E)末端分别比侧端的大3.56和3.72 kJ/mol,表明末端复合物稍占优势。甲酸与乙脒和苄脒的复合物的相互作用能(∆E)分别比四唑与乙脒和苄脒的复合物的大59.35和58.99 kJ/mol,表明脒与甲酸形成复合物时相互作用更强。溶剂DMSO的作用使得所有复合物的相互作用能变小,但脒与四唑的相互作用仍比脒与甲酸的弱。前者的结合常数与后者的相比只有1/315（乙脒）和1/218（苄脒）,这与实验结果相一致。     

Specificities and origins of the Slovak nomenclature of inorganic chemistry

Nowadays the discussion on the symbiosis of the international and national nomenclature systems in different areas of science provides clear evidences that full implementation of conventional international (mainly English) nomenclature principles in the local ones is sometimes not only unnecessary, but even redundant or impossible. Rapid development of natural sciences necessitates creation of accurate, comprehensive and comprehensible nomenclature systems for objects and phenomena under research. This study outlines the origins and development of the Slovak chemical nomenclature which is based on the Czech model. We analyze the unique Slovak nomenclature items as well as the re-evaluation of linguistic means in the field of inorganic chemistry in the international context. A part of this work is devoted to the syntactical structure of the names of inorganic compounds. At the same time we draw a parallel between chemical nomenclature and the phenomenon of controlled language.     

Theoretical modeling of the benzoic acid adsorption on the GaAs (001)-β2(2 × 4) oxidized surface

We describe a computational model of benzoic acid adsorbed on the most abundant and technologically important GaAs surface. The performances of many electronic devices based on organic layers deposited on semiconductor surfaces, critically depend on the quality of the layer, and thus on the features of the organic/inorganic bonds. Since very few is known about the atomic structure of such interfaces, theoretical modeling plays a central role in understanding these systems at the microscopic scale. We have optimized the structures of several clusters mimicking the unoxidized and oxidized GaAs (001) surface, using them to study the preferred arrangements of adsorbed benzoic acid molecules. The largest clusters were also used to investigate the cooperative effects between two adsorbed molecules, obtaining the most likely structure for a perfectly packed layer. Finally, we show the correlation of a microscopic observable, namely the energy of the lowest lying empty orbital concentrated on the organic moiety, with the electron affinity measured for para-substituted benzoic acids adsorbed on GaAs.     

Nanoarchitectonics on Electrosynthesis and Assembly of Conjugated Metallopolymers

In contrast to edge-on and face-on orientations, end-on uniaxial conjugated polymers have the theoretical possibility of providing a macroscopic crystalline film. However, their fabrication is insurmountable due to sluggishly thermodynamic equilibrium states. Herein, we report the programmatic pathway to fabricate nanoarchitectonics on end-on uniaxial conjugated metallopolymers by surface-initiated simultaneous electrosynthesis and assembly. Self-assembled monolayer (SAM) with bottom-up oriented electroactive molecules as a temple allows orientation, stacking, and reactive addition of monomers triggered by switching alternative redox reactions as well as crystallization of small molecules. Repeating the same reaction can repair the unreactive site on the SAM and dynamically and statistically ensure maximum iterative coverage with ideal linear coefficients between optical or electrical responses and iterative times. The resulting nanoarchitectonics on uniaxially assembled end-on polymers over centimeter-sized areas have a subnanometer-uniform morphology and exhibit ultrahigh modulus as well as an inorganic indium tin oxides and the highest conductance among conjugated molecular monolayers. Their memristive devices provide quantitative electrical and optical responses as a function of molecular length, bias, and iterative junctions. Precise processing of nanoarchitectonics as an electrically assisted assembly or printing technique can present sophisticated optoelectric functions and dimensional batch-to-batch consistency for micro-sized organic materials and electronics.     

Titanium oxide complexes with dinitrogen. Formation and characterization of the side-on and end-on bonded titanium oxide-dinitrogen complexes in solid neon

The reactions of titanium oxide molecules with dinitrogen have been studied by matrix isolation infrared spectroscopy. The titanium monoxide molecule reacts with dinitrogen to form the TiO(N(2))(x) (x = 1-4) complexes spontaneously on annealing in solid neon. The TiO(η(1)-NN) complex is end-on bonded and was predicted to have a (3)A' ground state arising from the (3)Δ ground state of TiO. Argon doping experiments indicate that TiO(η(1)-NN) is able to form complexes with one or more argon atoms. Argon atom coordination induces a large red-shift of the N-N stretching frequency. The TiO(η(2)-N(2))(2) complex was characterized to have C(2v) symmetry, in which both the N(2) ligands are side-on bonded to the titanium metal center. The tridinitrogen complex TiO(η(1)-NN)(3) most likely has C(3v) symmetry with three end-on bonded N(2) ligands. The TiO(η(1)-NN)(4) complex was determined to have a C(4v) structure with four equivalent end-on bonded N(2) ligands. In addition, evidence is also presented for the formation of the TiO(2)(η(1)-NN)(x) (x = 1-4) complexes, which were predicted to be end-on bonded.