Are matrix isolated species really “isolated”? Infrared spectroscopic and theoretical studies of noble gas-transition metal oxide complexes

In this review, we summarize our recent results on matrix isolation infrared spectroscopic studies and theoretical investigations of noble gas-transition metal oxide complexes. The results show that some transition metal oxide species trapped in solid noble gas matrices are chemically coordinated by one or multiple noble gas atoms forming noble gas complexes and, hence, cannot be regarded as isolated species. Noble gas coordination alters the vibrational frequencies as well as the geometric and electronic structures of transition metal oxide species trapped in solid noble gas matrixes. The interactions between noble gas atoms and transition metal oxides involve ion-induced dipole interactions as well as chemical bonding interactions. Periodic trends in the bonding in these noble gas-transition metal complexes are discussed.     

Noble gas-transition-metal complexes: coordination of VO2 and VO4 by Ar and Xe atoms in solid noble gas matrixes

The matrix isolation infrared spectroscopic and quantum chemical calculation results indicate that vanadium oxides, VO2 and VO4, coordinate noble gas atoms in forming noble gas complexes. The results showed that VO2 coordinates two Ar or Xe atoms and that VO4 coordinates one Ar or Xe atom in solid noble gas matrixes. Hence, the VO2 and VO4 molecules trapped in solid noble gas matrixes should be regarded as the VO2(Ng)2 and VO4(Ng) (Ng = Ar or Xe) complexes. The total V-Ng binding energies were predicted to be 12.8, 18.2, 5.0, and 7.3 kcal/mol, respectively, for the VO2(Ar)2, VO2(Xe)2, VO4(Ar), and VO4(Xe) complexes at the CCSD(T)//B3LYP level of theory.     

Noble gas-transition metal complexes: coordination of ScO+ by multiple Ar, Kr, and Xe atoms in noble gas matrixes

The combination of matrix isolation infrared spectroscopic and density functional calculation results provides strong evidence that the transition metal monoxide cation, ScO+, coordinates five noble gas atoms in forming the [ScO(Ng)5]+ (Ng = Ar, Kr, or Xe) complexes in noble gas matrixes.     

Coordination of niobium and tantalum oxides by Ar, Xe and O2: Matrix isolation infrared spectroscopic and theoretical study of NbO2(Ng)2 (Ng = Ar, Xe) and MO4(X) (M = Nb, Ta; X = Ar, Xe, O2) in solid argon

The combination of matrix isolation infrared spectroscopic and quantum chemical calculation results indicate that the NbO₂ molecule is coordinated by two noble gas atoms in forming the NbO₂(Ng)₂ (Ng = Ar, Xe) complexes in solid noble gas matrixes. In contrast, the TaO₂ molecule is not able to form similar noble gas complex. The niobium and tantalum dioxides further react with dioxygen to form the side-on bonded superoxo-dioxide complexes MO₄ (M = Nb, Ta), which are coordinated by one argon atom in solid argon matrix. The coordinated Ar atom in MO₄(Ar) can be replaced by O₂ or Xe in forming the MO₆ and MO₄(Xe) complexes. The results indicate that the NbO₂, NbO₄ and TaO₄ molecules trapped in solid noble gas matrixes should be regarded as the NbO₂(Ng)₂ and MO₄(Ng) (Ng = Ar, Xe; M = Nb, Ta) complexes instead of “isolated” metal oxide species.     

How strong is the interaction between a noble gas atom and a noble metal atom in the insertion compounds MNgF (M=Cu and Ag, and Ng=Ar, Kr, and Xe)?

Ab initio molecular orbital calculations have been carried out to investigate the structure and the stability of noble gas insertion compounds of the type MNgF (M=Cu and Ag, and Ng=Ar, Kr, and Xe) through second order Moller-Plesset perturbation method. All the species are found to have a linear structure with a noble gas-noble metal bond, the distance of which is closer to the respective covalent bond length in comparison with the relevant van der Waals limit. The dissociation energies corresponding to the lowest energy fragmentation products, MF+Ng, have been found to be in the range of -231 to -398 kJ/mol. The respective barrier heights pertinent to the bent transition states (M-Ng-F bending mode) are quite high for the CuXeF and AgXeF species, although for the Ar and Kr containing species the same are rather low. Nevertheless the M-Ng bond length in MNgF compounds reported here is the smallest M-Ng bond ever predicted through any experimental or theoretical investigation, indicating strongest M-Ng interaction. All these species (except AgArF) are found to be metastable in their respective potential energy surface, and the dissociation energies corresponding to the M+Ng+F fragments have been calculated to be 30.1-155.3 kJ/mol. Indeed, in the present work we have demonstrated that the noble metal-noble gas interaction strength in MNgF species (with M=Cu and Ag, and Ng=Kr and Xe) is much stronger than that in NgMF systems. Bader's [Atoms in molecules-A Quantum Theory (Oxford University Press, Oxford, 1990)] topological theory of atoms in molecules (AIM) has been employed to explore the nature of interactions involved in these systems. Geometric as well as energetic considerations along with AIM results suggest a partial covalent nature of M-Ng bonds in these systems. The present results strengthen our earlier work and further support the proposition on the possibility of experimental identification of this new class of insertion compounds of noble gas atoms containing noble gas-noble metal bond.     

Coordination of ScO+ and YO+ by multiple Ar, Kr, and Xe atoms in noble gas matrixes: a matrix isolation infrared spectroscopic and theoretical study

The combination of matrix isolation infrared spectroscopic and quantum chemical calculation results provide strong evidence that scandium and yttrium monoxide cations, ScO+ and YO+, coordinate multiple noble gas atoms in forming noble gas complexes. The results showed that ScO+ coordinates five Ar, Kr, or Xe atoms, and YO+ coordinates six Ar or Kr and five Xe atoms in solid noble gas matrixes. Hence, the ScO+ and YO+ cations trapped in solid noble gas matrixes should be regarded as the [ScO(Ng)5]+ (Ng = Ar, Kr, or Xe), [YO(Ng)6]+ (Ng = Ar or Kr) or [YO(Xe)5]+ complexes. Experiments with dilute krypton or xenon in argon or krypton in xenon produced new IR bands, which are due to the stepwise formation of the [ScO(Ar)(5-n)(Kr)n]+, [ScO(Kr)(5-n)(Xe)n]+ (n = 1-5), [YO(Ar)(6-n)(Kr)n]+ (n = 1-6), and [YO(Ar)(6-n)(Xe)n]+ (n = 1-4) complexes.     

Identification of the matrix shift: a fingerprint for neutral neon complex?

Ar-NiCO and Ne-NiCO have been predicted as novel neutral noble gas charge-transfer complexes, with binding energies of 7.70 and 2.16 kcal/mol, respectively, by the highly correlated coupled-cluster singles and doubles including a perturbational estimate of triple excitations calculations. The calculated shifts in the Ni-C-O bending frequency are 48 and 36 cm(-1) for Ar-NiCO and Ne-NiCO, while the corresponding experimental matrix shifts are 46 and 36 cm(-1), respectively. The anharmonicity effects for these frequencies are verified to be very small. The interaction between a noble gas atom and NiCO is discussed through natural population analyses and the electron density difference map. We further examined the noble gas matrix effects on the geometrical structure and vibrational frequencies of NiCO by performing density functional theory calculations for the Ng31-NiCO (Ng = Ar, Ne, He) system. The present results will inspire the further experimental investigation on the complexes of noble gas and transition metal compounds generated in the matrix isolation experiments.     

Matrix isolation infrared spectroscopic and theoretical study of noble gas coordinated rhodium-dioxygen complexes

Reactions of rhodium atoms with dioxygen molecules in solid argon have been investigated using matrix isolation infrared absorption spectroscopy. The rhodium-dioxygen complexes, Rh(eta2-O2), Rh(eta2-O2)2, and Rh(eta2-O2)2(eta1-OO), are produced spontaneously on annealing. The Rh(eta2-O2) complex rearranges to the inserted RhO2 molecule under visible light irradiation. Experiments doped with xenon in argon show that the rhodium-dioxygen complexes are coordinated by one or two noble gas atoms in solid noble gas matrixes. Hence, the Rh(eta2-O2), Rh(eta2-O2)2, and Rh(eta2-O2)2(eta1-OO) molecules trapped in solid noble gas matrixes should be regarded as the Rh(eta2-O2)(Ng)2, Rh(eta2-O2)2(Ng)2, and Rh(eta2-O2)2(eta1-OO)(Ng) (Ng = Ar or Xe) complexes. The product absorptions are identified on the basis of isotopic substitution and density functional theory calculations.     

Electronic structure of oxide, peroxide, and superoxide clusters of the 3d elements: a comparative density functional study

The 3d-element transition metal dioxide MO(2), peroxide M(O(2)), and superoxide MOO clusters (M=Sc-Zn), are studied by density functional theory with the B1LYP functional. The reliability of the methods and basis sets employed was tested by a reinvestigation of the monoxides, for which a database of experimental data is available. The global minima on the M+O(2) potential energy surfaces correspond to dioxide structure, the only exception being CuOO, with a superoxide structure. All Zn dioxygen clusters are thermodynamically unstable-their ground states lie higher than the dissociation limit to Zn+O(2). Our calculations are in favor of the high-spin configurations for the FeO(2), CoO(2), and NiO(2) ground states, which are still a subject of extensive theoretical and experimental studies. These assignments are confirmed by the coupled-cluster method, CCSD(T), except for NiO(2). Based on the existence of a stable NiO(2) monoanion in a (4)B(1) state, however, it can be concluded that NiO(2) in its (5)A(1) state should also be stable. The vibrational frequencies are calculated for clusters entrapped in the cubic cell of solid Ar matrix and compared with those obtained for gas-phase clusters. The matrix has no influence on the vibrations of the monoxides and most of the dioxides; however, Co and Ni-dioxoclusters interact strongly with the atoms from the noble gas matrix. The most intense frequencies in the IR spectra are shifted to lower energies and the ordering of the low-lying electronic states by stability is also reversed. According to the electrostatic potential maps, the oxygen atoms in the peroxides are more nucleophilic than those in the dioxides and superoxides. The terminal oxygen atom in superoxides is more nucleophilic than its M-bonded oxygen atom, though charge distribution analysis predicts a smaller negative charge on the terminal oxygen. TiO(2) is the only dioxide in which nucleophilic character in the vicinity of the metal cation is induced.     

A noble interaction: An assessment of noble gas binding ability of metal oxides (metal = Cu,Ag, Au)

An in silico study is performed on the structure and the stability of noble gas (Ng) bound MO complexes (M = Cu, Ag, Au). To understand the stability of these Ng bound complexes, dissociation energies, dissociation enthalpy, and dissociation free energy change are computed. The stability of NgMO is also compared with that of the experimentally detected NgMX (X= F, Cl, Br). It is found that MO has lower Ng binding ability than that of MX. All the dissociation processes producing Ng and MO are endothermic in nature and for the Kr‐Rn bound MO (M = Cu, Au), and Xe and Rn bound AgO cases, the corresponding dissociation processes are turned out to be endergonic in nature at standard state. The Wiberg bond indices of Ng? M bonds and Ng→M electron transfer gradually increase from Ar to Rn and for the same Ng they follow the order of NgAuO > NgCuO > NgAgO. Energy decomposition analysis shows that the Ng? M bonds in NgMO are partly covalent and partly electrostatic in nature. Electron density analysis further highlights the partial covalent character in Ng? M bonds. © 2016 Wiley Periodicals, Inc.     

Matrix isolation spectroscopic and theoretical study of water adsorption and hydrolysis on molecular tantalum and niobium oxides

The reactions of molecular tantalum and niobium monoxides and dioxides with water were investigated by matrix isolation infrared spectroscopy. In solid neon, the metal monoxide and dioxide molecules reacted with water to form the MO(H(2)O) and MO(2)(H(2)O) (M = Ta, Nb) complexes spontaneously on annealing. The MO(H(2)O) complexes photochemically rearranged to the more stable HMO(OH) isomers via one hydrogen atom transfer from water to the metal center under visible light excitation. In contrast, the MO(2)(H(2)O) complexes isomerized to the more stable MO(OH)(2) molecules via a hydrogen atom transfer from water to one of the oxygen atoms of metal dioxide upon visible light irradiation. The aforementioned species were identified by isotopic-substituted experiments as well as density functional calculations.     

Transition metal-boron complexes BnM: from bowls (n = 8-14) to tires (n = 14)

Transition metal-boron complexes BnM have been predicted at density functional theory level to be molecular bowls (n = 8-14) hosting a transition metal atom (M) inside or molecular tires (n = 14) centered with a transition metal atom. Small Bn clusters prove to be effective inorganic ligands to all the VB-VIIIB transition metal elements in the periodic table. Density functional evidences obtained in this work strongly suggest that bowl-shaped fullerene analogues of Bn units exist in small BnM complexes and the bowl-to-tire structural transition occur to the first-row transition metal complexes BnM (M = Mn, Fe, Co) at n = 14, a size obviously smaller than n = 20 where the 2D-3D structural transition occurs to bare Bn. The half-sandwich-type B12Cr (C3v), full sandwich-type (B12)2Cr (D3d), bowl-shaped B14Fe (C2), and tire-shaped B14Fe (D7d) and B14Fe- (C7v) are the most interesting prototypes to be targeted in future experiments. These BnM complexes may serve as building blocks to form extended boron-rich BnMm tubes or cages (m > or = 2) or as structural units to be placed inside carbon nanotubes with suitable diameters.     

Agostic interaction in the methylidene metal dihydride complexes H2MCH2 (M=Y, Zr, Nb, Mo, Ru, Th, or U)

Multiconfigurational quantum chemical methods (complete active space self-consistent field (CASSCF)/second-order perturbation theory (CASPT2)) have been used to study the agostic interaction between the metal atom and H(C) in the methylidene metal dihydride complexes H2MCH2, where M is a second row transition metal or the actinide atoms Th or U. The geometry of some of these complexes is highly irregular due to the formation of a three center bond CH...M, where the electrons in the CH bond are delocalized onto empty or half empty orbitals of d- or f-type on the metal. No agostic interaction is expected when M=Y, where only a single bond with methylene can be formed, or when M=Ru, because of the lack of empty electron accepting metal valence orbitals. The largest agostic interaction is found in the Zr and U complexes.     

Theoretical study on structures and vibrational spectra of M+(H2O)Ar (M = Cu,Ag, Au)

A theoretical study on the structures and vibrational spectra of M⁺(H₂O)Ar_0‐1 (M = Cu, Ag, Au) complexes was performed using ab initio method. Geometrical structures, binding energies (BEs), OH stretching vibrational frequencies, and infrared (IR) absorption intensities are investigated in detail for various isomers with Ar atom bound to different binding sites of M⁺(H₂O). CCSD(T) calculations predict that BEs are 14.5, 7.5, and 14.4 kcal/mol for Ar atom bound to the noble metal ion in M⁺(H₂O)Ar (M = Cu, Ag, Au) complexes, respectively, and the corresponding values have been computed to be 1.5, 1.3, and 2.1 kcal/mol when Ar atom attaches to a H atom of water molecule. The former structure is predicted to be more stable than the latter structure. Moreover, when compared with the M⁺(H₂O) species, tagging Ar atom to metal cation yields a minor perturbation on the IR spectra, whereas binding Ar atom to an OH site leads to a large redshift in OH stretching vibrations. The relationships between isomers and vibrational spectra are discussed. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Noble gas-actinide complexes of the CUO molecule with multiple Ar,Kr, and Xe atoms in noble-gas matrices

Laser-ablated U atoms react with CO in excess argon to produce CUO, which is trapped in a triplet state in solid argon at 7 K, based on agreement between observed and relativistic density functional theory (DFT) calculated isotopic frequencies ((12)C(16)O, (13)C(16)O, (12)C(18)O). This observation contrasts a recent neon matrix investigation, which trapped CUO in a linear singlet state calculated to be about 1 kcal/mol lower in energy. Experiments with krypton and xenon give results analogous to those with argon. Similar work with dilute Kr and Xe in argon finds small frequency shifts in new four-band progressions for CUO in the same triplet states trapped in solid argon and provides evidence for four distinct CUO(Ar)(4-n)(Ng)(n) (Ng = Kr, Xe, n = 1, 2, 3, 4) complexes for each Ng. DFT calculations show that successively higher Ng complexes are responsible for the observed frequency progressions. This work provides the first evidence for noble gas-actinide complexes, and the first example of neutral complexes with four noble gas atoms bonded to one metal center.     

Bonding analysis for NgAuOH (Ng = Kr,Xe)

Noble‐gas‐noble‐metal hydroxides NgAuOH (Ng = Kr, Xe) are investigated at the MP2 theoretical level. All species are found to be in Cs symmetry with an approximate linear Ng? Au? O moiety. The noble‐gas‐noble‐metal bond lengths are comparable with covalent limits, and the corresponding binding energies have been computed to be 59.6 and 83.4 kJ/mol for KrAuOH and XeAuOH, respectively. Except the charge‐induced dipole contribution to the binding energies, the remainder could be ascribed to the higher‐order charge‐induction energies, dispersion energies, the contributions of multipole moments on AuOH and covalent effects. The title species are sufficiently chemical bound and are expected to be stable species theoretically. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Die Reaktionen der Benzoyl-und Salicoylhydrazone des Vanillins,Furfurols und Zimtaldehyds mit zweiwertigen Ionen der Übergangsmetalle

The reaction of benzoyl and salicoylhydrazones of vanilline, furfural, and cinnamaldehyde with some divalent metal ions of the first transition series is investigated. The structure of the ligand in the solid chelates is studied by IR-spectrophotometry which showed that the ligand is coordinated to the central metal ion through the oxygen atom of the C=O and nitrogen atom of the C=N group. Spectrophotometric, and conductometric studies were carried out to investigate the stoichiometry of the complexes under consideration. The shifts in the C=O and C=N IR-bands are utilised for the determination of the coordination bond length.

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THE CHEMISTRY OF (ECN)2 (E = S,Se) AND RELATED COMPOUNDS

The psuedohalogens (ECN)₂ (E = S, Se) have been prepared by reaction of AgNCS with bromine and AgNCSe with iodine respectively. (SCN)₂ spontaneously polymerises to give polythiocyanogen a polymer of unknown structure with empirical formula (SCN)_x. A series of late transition metal complexes bearing the ambidentate psuedohalide ligands (ECN) (E = S, Se) have been synthesised. In addition we have prepared a series of late transition metal complexes of the cyanodithioimidocarbonate ion [C₂N₂S₂]^2? and the first transition metal complexes of the cyanodiselenocarbonate ion [C₂N₂Se₂]^2?.     

Fluorescence spectra of matrix isolated silver atoms

Silver atoms isolated in noble gas matrices show fluorescence spectra with large Stokes shifts, when optically excited via the 5P ← 5S transition which is three-fold split in the matrix by spin—orbit and crystal field interaction. The shifts are explained by the formation of an excimeric bond between the excited metal atom and the noble gas cage. For Ag in Kr it is demonstrated, that most of the Stokes shift arises from the ground state repulsion.     

Microwave spectra and structures of KrAuF, KrAgF, and KrAgBr; 83Kr nuclear quadrupole coupling and the nature of noble gas-noble metal halide bonding

Microwave spectra of the complexes KrAuF and KrAgBr have been measured for the first time using a cavity pulsed jet Fourier transform microwave spectrometer. The samples were prepared by laser ablation of the metal from its solid and allowing the resulting plasma to react with an appropriate precursor (Kr, plus SF6 or Br2) contained in the backing gas of the jet (usually Ar). Rotational constants; geometries; centrifugal distortion constants; vibration frequencies; and 197Au, 79Br, and 81Br nuclear quadrupole coupling constants have all been evaluated. The complexes are unusually rigid and have short Kr-Au and Kr-Ag bonds. The 197Au nuclear quadrupole coupling constant differs radically from its value in an AuF monomer. In addition 83Kr hyperfine structure has been measured for KrAuF and the previously reported complex KrAgF. The geometry of the latter has been reevaluated. Large values for the 83Kr nuclear quadrupole coupling constants have been found for both complexes. Both the 197Au and 83Kr hyperfine constants indicate a large reorganization of the electron distribution on complex formation. A thorough assessment of the nature of the noble gas-noble metal bonding in these and related complexes (NgMX; Ng is a noble gas, M is a noble metal, and X is a halogen) has been carried out. The bond lengths are compared with sums of standard atomic and ionic radii. Ab initio calculations have produced dissociation energies along with Mulliken populations and other data on the electron distributions in the complexes. The origins of the rigidity, dissociation energies, and nuclear quadrupole coupling constants are considered. It is concluded that there is strong evidence for weak noble gas-noble metal chemical bonding in the complexes.