Experimental and Theoretical Studies of the Infrared Spectra and

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Experimental and Theoretical Studies of the Infrared Spectra and Bonding Properties of NgBeCO and a Comparison with NgBeO (Ng = He, Ne, Ar, Kr, Xe) 3

Qingnan Zhang, Mohua Chen, Mingfei Zhou, Diego Marcelo Andrada, and Gernot Frenking J. Phys. Chem. A, Just Accepted Manuscript • DOI: 10.1021/jp509006u • Publication Date (Web): 16 Oct 2014 Downloaded from http://pubs.acs.org on October 24, 2014

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The Journal of Physical Chemistry

Experimental and Theoretical Studies of the Infrared Spectra and Bonding Properties of NgBeCO3 and a Comparison with NgBeO (Ng = He, Ne, Ar, Kr, Xe)

Qingnan Zhang†, Mohua Chen†, Mingfei Zhou†,*, Diego M. Andrada‡, Gernot Frenking‡,* †

Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai 200433, China. Tel: +86-21-51630208 ‡ Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse, D-35043 Marburg, Germany. Tel: +49-6421-2825563

This paper is dedicated to Markku Räsänen on the occasion of his 65th birthday

Abstract. The novel neon complex NeBeCO3 has been prepared in a low-temperature neon matrix via co-deposition of laser-evaporated beryllium atoms with O2 + CO/Ne. Doping by the heavier noble gas atoms argon, krypton and xenon yielded the associated adducts NgBeCO3 (Ng = Ar, Kr, Xe). The noble gas complexes have been identified via infrared spectroscopy. Quantum chemical calculations of NgBeCO3 and NgBeO (Ng = He, Ne, Ar, Kr, Xe) using ab initio methods and density functional theory show that the Ng-BeCO3 bonds are slightly longer and weaker than the Ng-BeO bonds. The energy decomposition analysis of the Ng-Be bonds suggests that the attractive interactions come mainly from the Ng→BeCO3 and Ng→BeO σ donation.

Keywords: Noble Gas Compounds; Donor-Acceptor Bonds; Matrix-Isolation Studies; Quantum Chemical Calculations; Bonding Analysis

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Introduction The long taught paradigm that the noble gas elements cannot form stable molecules in a condensed phase was disproved in 1962, when three groups independently1 isolated noble gas compounds within a three months period.2-4 The first report came from N. Bartlett,2 who reported the synthesis of a compound which was originally assigned with the formula XePtF6.5 The second publication came from R. Hoppe3 who prepared the first binary noble gas compound XeF2. Two months later the group of Claasen, Selig and Malm4 synthesized the xenon(IV) species XeF4. In the same year, the synthesis of the first radon compound RnF2 was reported by Fields, Stein and Zirin6 while the first krypton compound KrF2 was prepared by Turner and Pimentel one year later.7 Nowadays, a large number of noble gas compounds containing the heavy atoms Xe, Kr and Rn are known.8-11

The lighter homologues He, Ne and Ar proved to be much more difficult for forcing them into chemical bonding. A theoretical study suggested in 1989 that the ArF+ cation which has a strong covalent Ar+-F bond with an estimated bond dissociation energy Do = 49 + 3 kcal/mol might become isolated in the presence of weakly coordinating anions.12 The theoretical prediction has not become verified until today. A different approach led finally to the isolation of the first stable argon compound. In the year 2000, the group of Khriachtchev, Pettersson, Runeberg, Lundell, and Räsänen reported about the synthesis of HArF in a low-temperature argon matrix.13 The authors photolyzed HF embedded in solid argon which reacted with hydrogen and fluorine atoms yielding the triatomic species HArF. The molecule could be identified by vibrational spectroscopy and by comparing the experimentally observed spectra with ab initio calculations of the vibrational modes. The same technique had previously been used in the group of Räsänen for the synthesis of numerous xenon and krypton compounds14-18 with the general formula HNgY (Ng = Xe, Kr; Y = electron-withdrawing group) which could then successfully be expanded to Ng = Ar. Numerous other species of the type HNgY (Ng = Ar, Kr, Xe) have later been synthesized.19

Another approach for binding noble gas atoms in molecules utilizes their donor properties 2


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in donor-acceptor complexes with strong Lewis acids. The first successful effort came in 1975 from Perutz and Turner who provided evidence for the formation of weakly bonded adducts (CO)5TMNg (TM = Cr, Mo, W; Ng = Ne, Ar, Kr, Xe) in low-temperature matrices.20-22 Measurements of the temperature dependence of the dissociation rate constants of (CO)5TM-Xe in the gas phase by Wells and Weitz made it possible to estimate the bond dissociation energies (BDEs) for TM = Cr (9.0 + 0.9 kcal/mol), TM = Mo (8.0 + 1.0 kcal/mol), and TM = W (8.2 + 1.0 kcal/mol) and upper limits for the BDEs of (CO)5W-Kr (< 6.0 kcal/mol) and (CO)5W-Ne (< 3

kcal/mol).23 The BDE of (CO)5W-Xe has also been

measured in liquid xenon (8.4 + 0.2 kcal/mol)24 and in supercritical CO2 (8.2 + 0.2 kcal/mol)24 which is in excellent agreement with the earlier result.20-22 Quantum chemical calculations of (CO)5TMNg (TM = Cr, Mo, W; Ng = Ar, Kr, Xe), which gave BDEs in agreement with the experimental values showed that the noble gas atoms are bonded through van der Waals forces rather than genuine chemical bonds.25

The search for donor-acceptor complexes with noble gas atoms as donor species was boosted in 1986 when a quantum chemical study predicted that the Lewis acid BeO binds a helium atom in the complex HeBeO with an unprecedented bond strength of ~3 kcal/mol.26-27 Further theoretical work suggested that BeO might be the strongest neutral Lewis acid of main group atoms which binds noble gas atoms He - Xe with rather large BDEs up to De = 15.8 kcal/mol for XeBeO.28-32 The complexes ArBeO, KrBeO, and XeBeO were later prepared by Andrews and coworkers in low-temperature matrix experiments.33

The authors

also reported about the synthesis of both isomers of the carbonyl complex OCBeO and COBeO34 which had been predicted as stable species with rather large BDEs of De = 43.3 kcal/mol and De = 20.4 kcal/mol, respectively.35-37 A remarkable feature of OCBeO is the rather strong blue shift of the C-O stretching frequency toward higher wave numbers compared with free CO of 43 cm-1.34

The finding that BeO is an unusually strong σ acceptor led to a search for other beryllium containing species which might further enhance the Lewis acidity of the acceptor fragment.38-43 Recently, we reported about the preparation and isolation of the OCBeCO3 3



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complex in a low-temperature neon matrix.44 The OCBeCO3 complex has a very high C-O stretching frequency of 2263 cm-1, which is blue-shifted by 122 cm-1 with respect to free CO and 79 cm-1 higher than in OCBeO. This implies that beryllium carbonate BeCO3 is a strong Lewis acid which exhibits unusual acceptor properties. Quantum chemical calculations at the CCSD(T) level showed that OCBeCO3 has a slightly smaller BDE (De = 28.8 kcal/mol) than OCBeO (De = 37.6 kcal/mol). The bigger C-O stretching frequency in OCBeCO3 than in OCBeO was explained with the occurrence of some OC←BeO π-backdonation while the OC←BeCO3 π-backdonation is negligible.44 We decided to carry out a comparative study of the noble gas complexes NgBeCO3 and NgBeO. Here we report a matrix isolation experimental preparation and spectroscopic identification of BeCO3 in solid neon matrix, which is characterized to be coordinated by a neon atom as NeBeCO3. The heavier NgBeCO3 complexes (Ng = Ar, Kr, Xe) are also produced in solid neon. We also report about quantum chemical calculations of the equilibrium geometries, bond dissociation energies and vibrational spectra of the whole set of NgBeCO3 and NgBeO complexes (Ng = He, Ne, Ar, Kr, Xe). The nature of the noble gas bonds Ng-BeCO3 and Ng-BeO has been investigated with an energy decomposition analysis.

Experimental Methods The beryllium carbonate NgBeCO3 complexes were prepared by reactions of beryllium atoms with carbon monoxide and dioxygen mixtures in solid neon. The beryllium atoms were produced by pulsed-laser evaporation of a beryllium metal target. The experimental apparatus for pulsed laser evaporation-matrix isolation infrared spectroscopy has been described in detail previously.45-46 Briefly, the 1064 nm Nd:YAG laser fundamental wavelength (Continuum, Minilite II; 10 Hz repetition rate) was focused onto a rotating beryllium metal target. The laser evaporated beryllium atoms were co-deposited with CO/O2 reagent gas in excess neon onto a cryogenic window, which was maintained at 4 K by means of a closed-cycle helium refrigerator. The samples were usually deposited for 30 min to one hour at a rate of approximately 4 mmol/h. The CO/O2/Ne mixtures were prepared in a stainless steel vacuum line using standard manometric technique. O2 and CO (Shanghai BOC, >99.5%) and isotopic-labeled 13CO, C18O and 18O2 (ISOTEC, 99%) were used without 4


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further purification. The as-deposited samples were subjected to annealing and photolysis experiments to initiate diffuse and photo-induced reactions. The infrared absorption spectra of the products in the mid-infrared region (4000-450 cm-1) were recorded on a Bruker Vertex 80V spectrometer at 0.5 cm-1 resolution using a liquid nitrogen cooled HgCdTe (MCT) detector. The heavier NgBeCO3 complexes were prepared using mixtures of neon doped with heavier noble gas atoms as a matrix. The coordinated neon atom in NeBeCO3 can be substituted by heavier noble gas atoms when annealing the solid matrix sample in forming the NgBeCO3 complexes with Ng=Ar, Kr, Xe.

Theoretical Methods All geometry optimizations have been carried out at the M06-2X/def2-TZVPP47-48, MP2/cc-pVTZ49-52 and CCSD(T)/cc-pVTZ51-53 levels of theory. The stationary points were located with the Berny algorithm54 using redundant coordinates. Analytical Hessians were computed to determinate the nature of the stationary points and to describe the IR spectra.55 The harmonic vibrational frequencies were computed at each level of theory. The DFT calculations were performed using Gaussian 0956 while the ab initio calculations were carried out using MOLPRO 2012.57-58

For the bonding analyses we calculated the molecules using the gradient corrected functional BP8659-60 in conjunction with the Grimme dispersion corrections (BP86-D3)61 using uncontracted Slater-type orbitals (STOs) as basis functions.62 The latter basis sets for all elements have triple-ζ quality augmented by two sets of polarization functions (ADF-basis set TZ2P+). This level of theory is denoted BP86/TZ2P+. An auxiliary set of s, p, d, f, and g STOs was used to fit the molecular densities and to represent the Coulomb and exchange potentials accurately in each SCF cycle.63 The BP86/TZ2P+ calculations were performed using

the

CCSD(T)/cc-pVTZ

optimized

geometries

with

the

program

package

ADF2013.01.64

The interatomic interactions were investigated by means of an energy decomposition analysis (EDA, also termed extended transition state method - ETS) developed independently 5



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by Morokuma65 and by Ziegler and Rauk.66 The bonding analysis focuses on the instantaneous interaction energy ∆Eint of a bond A–B between two fragments A and B in the particular electronic reference state and in the frozen geometry of AB. This interaction energy is divided into three main components [Eq. (1)].

∆Eint = ∆Eelstat + ∆EPauli + ∆Eorb

(1)

The term ∆Eelstat corresponds to the quasiclassical electrostatic interaction between the unperturbed charge distributions of the prepared atoms and is usually attractive. The Pauli repulsion ∆EPauli is the energy change associated with the transformation from the superposition of the unperturbed electron densities ρ A + ρ B of the isolated fragments to the ˆ [ Ψ Ψ ] , which properly obeys the Pauli principle through explicit wavefunction Ψ 0 = N Α A B

ˆ operator) and renormalization (N = constant) of the product antisymmetrization ( Α wavefunction. ∆EPauli comprises the destabilizing interactions between electrons of the same spin on either fragment. The orbital interaction ∆Eorb accounts for charge transfer and polarization effects. The ∆Eorb term can be decomposed into contributions from each irreducible representation of the point group of the interacting system. Further details on the EDA/ETS method67 and its application to the analysis of the chemical bond68-71 can be found in the literature.

The EDA-NOCV72 method combines charge (NOCV) and energy (EDA) decomposition schemes to decompose the deformation density which is associated with the bond formation, ∆ρ, into different components of the chemical bond. The EDA-NOCV calculations provide pairwise energy contributions for each pair of interacting orbitals to the total bond energy. NOCV (Natural Orbital for Chemical Valence)73-74 is defined as the eigenvector of the valence operator,

, given by Equation (2): (2)

In the EDA-NOCV scheme the orbital interaction term, ∆Eorb, is given by Equation (3): 6


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(3) in which

and

are diagonal transition state Kohn-Sham matrix elements

corresponding to NOCVs with the eigenvalues -vk and vk, respectively. The

term of a

particular type of bond are assigned by visual inspection of the shape of the deformation density, ∆ρk. The EDA-NOCV scheme thus provides both qualitative (∆ρorb) and quantitative (∆Eorb) information about the strength of orbital interactions in chemical bonds, also in molecules with C1 symmetry.75-82

Experimental Results The experiments were performed using different ratios of CO/O2 mixtures in excess neon. The spectra in selected regions via co-deposition of laser-evaporated beryllium atoms with a 0.05% O2 + 0.025% CO/Ne sample are shown in Figure 1.

Figure 1

Besides the strong CO absorption at 2140.8 cm-1, absorptions due to beryllium carbonyls Be(CO)2 (1925.8 cm-1), Be(CO)3 (1948.0 cm-1), BeBeCO (1951.4 cm-1) and OCBeBeCO (1931.0 cm-1), and beryllium and dioxygen reaction products OBeO (1431.4 cm-1), OBeO+ (962.0/957.4 cm-1) and cyclic-Be2O2 (1155.8, 890.2 and 534.6 cm-1), as well as (CO)2(1517.7 cm-1)83 and O4- (973.1 cm-1)84 were observed after 30 min of sample deposition at 4 K (Figure 1, trace a). These beryllium carbonyl and oxide species were previously identified in the reactions of beryllium atoms with CO or O2 in solid argon.85-87 When the as-deposited sample was annealed to 12 K (Figure 1, trace b), the IR intensities of the Be(CO)2 and OBeO+ absorptions decreased while the IR intensities of the Be(CO)3, BeBeCO, OCBeBeCO and cyclic-Be2O2 absorptions increased. When the sample was subjected to subsequent broad band irradiation using a mercury arc lamp without a filter (250 < λ < 580 nm), the beryllium carbonyl absorptions were completely destroyed as well as the OBeO+ and (CO)2absorptions. The IR intensities due to cyclic-Be2O2 markedly increased with the production 7



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of a set of new absorptions at 1863.6, 1202.6, 1107.6, 867.3, 795.3, 779.9 and 745.2 cm-1 during broad band irradiation. These new absorptions were observed neither in the experiment using O2/Ne as reagent gas without CO doping nor in the experiment with CO/Ne sample without O2 doping. Experiments were also repeated using the isotopic-labeled mixture samples, the infrared spectra in selected regions with different isotopic samples are shown in Figures 2 and 3, respectively, with the isotopic counterparts summarized in Table 1.

Figures 2, 3; Table 1

The absorptions at 1863.6, 1202.6, 1107.6, 867.3, 795.3, 779.9 and 745.2 cm-1 were only produced in the mixed CO + O2/Ne experiments indicating that both CO and O2 are involved in the formation of this species. The band positions are very close to those BeCO3 related vibrations of OCBeCO3 (1852.2, 1199.2, 1122.2, 886.7, 804.2, 796.8 and 771.9 cm-1 in neon)20 with very similar 13-C and 18-O isotopic frequency shifts (Table 1), indicating that the absorber of these new absorptions is a beryllium carbonate BeCO3 species. The 1863.6 cm-1 absorption is due to the C=O stretching vibration. The 1202.6 cm-1 absorption belongs to a combination mode of antisymmetric OBeO and OCO stretching vibrations. The 1107.6 and 867.3 cm-1 absorptions are the symmetric OBeO and OCO stretching modes, respectively. The 795.3 and 779.9 cm-1 absorptions are attributed to the out-of-plane and in-plane bending vibrations, respectively. While the 745.2 cm-1 absorption is due to the scissoring vibration (Table 1).

Figure 4, Table 2

Our recent study indicates that beryllium carbonate BeCO3 can bind strongly with the CO ligand in forming the OCBeCO3 complex, which has a very high C-O stretching frequency of 2263 cm-1.46 This suggests that beryllium carbonate BeCO3 is a strong Lewis acid. It may also bind with noble gas atoms yielding stable noble gas complexes. To determine whether the BeCO3 molecule trapped in solid neon is coordinated by neon atoms or not and, if so, to determine also the number of neon atoms that bind intimately to BeCO3, experiments were 8


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performed using mixtures of neon doped with heavier noble gas atoms. The spectra in selected regions are shown in Figure 4. An additional red-shifted or blue-shifted absorption was produced when 0.025% argon was doped into neon for each mode of BeCO3. Similar spectral features were observed in the experiments with neon doped by krypton or xenon. These observations imply that BeCO3 coordinates one neon atom in solid neon matrix, and that the BeCO3 species trapped in solid neon should be regarded as NeBeCO3. The new absorptions produced in the heavier noble gas atom doping experiments are assigned to the NgBeCO3 complexes (Ng = Ar, Kr, Xe) in solid neon, as listed in Table 2. Note that the band positions of the three high-frequency modes (CO stretching, CO2 & BeO2 antisymmetric stretching, and BeO2 symmetric stretching) are red-shifted whereas the four low-frequency modes (CO2 symmetric stretching, CO3 in-plane and out-of-plane bending and BeO2 & CO2 scissoring) are blue-shifted when the neon atom is replaced by the heavier noble gas atoms. Theoretical Results Figure 5 shows the optimized geometries of the beryllium carbonate complexes NgBeCO3 (C2v) and the beryllium oxide homologues NgBeO (C∞v) along with the calculated bond lengths and angles at the M06-2X/def2-TZVPP, MP2/cc-pVTZ and CCSD(T)/cc-pVTZ levels of theory.

It is gratifying that the three different levels of theory give very similar

results. The largest differences are found for the Ng-BeCO3 distance which is predicted to be somewhat shorter at CCSD(T)/cc-pVTZ (1.799 Å) than at M06-2X/def2-TZVPP (1.842 Å). All methods agree that the Ng-BeCO3 bonds are a slightly longer than the Ng-BeO bonds. Figure 5 gives also the optimized geometries of the Lewis acids BeCO3 and BeO. A comparison of the calculated bond lengths and angles of the free species with the data of the complexes NgBeCO3 and NgBeO indicates that the geometries of the acceptor moieties change very little upon complexation.

Tables 3 - 5

Tables 3 - 5 show the calculated vibrational frequencies of NgBeCO3 and NgBeO at the three levels of theory. Experimental values are given in italics. Inspection of the largest 9



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values of the stretching modes (Be-O for NgBeO and C-O for NgBeCO3) shows that M06-2X/def2-TZVPP strongly overestimates the predicted frequency for the Be-O mode while MP2/cc-pVTZ underestimates the Be-O mode, but overestimates the C-O frequency. The CCSD(T)/cc-pVTZ values for the Be-O stretching mode in NgBeO in general are very close to the experimental data while the C-O stretching frequencies are similar to the MP2/cc-pVTZ data. More important than the absolute values is the shift of the vibrational frequencies. The experimental and calculated alterations of the fundamental modes of NgBeCO3 (Ng = Ar, Kr, Xe) with respect to NeBeCO3 are given in Table 6.

Table 6

There is a remarkably good agreement of the vibrational shifts for the fundamental modes (CO stretch, CO2 & BeO2 asym. stretch, BeO2 symm. stretch and CO3 out-of-plane bend) between the experimental data and the calculated results at all levels of theory. The calculated red shifts of the first three modes and the blue shifts of the CO3 out-of-plane bending and BeO2 & CO2 scissoring modes are within 5 cm-1 of the experimental data.

The experimental infrared spectrum could not detect a signal for the Ng-Be stretching mode in the complexes NgBeCO3. This can be explained with the calculated IR intensity which is essentially zero in all noble gas adducts (Tables 3 - 5). They might be observed in Raman spectra of the compounds, but they are predicted to have rather low frequencies. The CCSD(T)/cc-pVTZ values are between 372 cm-1 for Ng = He and 146 cm-1 for Ng = Xe (Table 5). All calculations give for the Ng-Be stretching mode in NgBeO and NgBeCO3 the same trend He > Ne > Ar > Kr > Xe which can be attributed to the Ng mass. The Ng-Be frequencies of NgBeO are for a given atom Ng always higher than for NgBeCO3.

Table 7

Table 7 shows the theoretically predicted BDEs of NgBeCO3 and NgBeO. The theoretically predicted De values and the ZPE (Zero Point vibrational Energy) corrected Do 10


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data at the three levels of theory agree quite well. The calculations suggest that the beryllium carbonate complexes NgBeCO3 have slightly weaker Ng-Be bonds than NgBeO. This is in accord with the slightly shorter Ng-BeO bonds compared with Ng-BeCO3. We want to point out, however, that shorter bonds are not always stronger than longer bonds between the same atoms.88-92 The calculations give the expected trend for the Ng-Be bond strength He < Ne < Ar < Kr < Xe in both sets of complexes. The strongest bond is predicted for Xe-BeO with a BDE of De = 15.9 kcal/mol at the CCSD(T)//CBS level which is in excellent agreement with the earlier value of 15.8 kcal/mol.30

Table 8

In Table 8 are gathered the results of the EDA-NOCV analysis of NgBeCO3 and NgBeO at the BP86-D3/TZ2P+ level using the CCSD(T)/cc-pVTZ optimized geometries. The BP86-D3 level makes it possible to separate dispersion interactions from genuine chemical bonding. The data suggest that the Ng-Be bonds comes mainly from the Ng→BeCO3 and Ng→BeO σ donation. The orbital interactions ∆Eorb provide between 72% (NeBeO) - 88% (XeBeCO3) of the total attraction between Ng and the acceptor moiety. The breakdown of the orbital terms indicates as expected that the orbital interactions are dominated by the σ donation ∆Eorb(a1). We want to point out that the attractive interactions which come mainly from ∆Eorb are considerably weakened by the Pauli repulsion ∆EPauli which arises from the forbidden overlap between doubly occupied orbitals.

Summary and Conclusion

The results of this work can be summarized as follows. The novel neon complex NeBeCO3 could be prepared in a low-temperature neon matrix via co-deposition of laser-evaporated beryllium atoms with O2 + CO/Ne. Doping by the heavier noble gas atoms argon, krypton and xenon yielded the associated adducts NgBeCO3 (Ng = Ar, Kr, Xe). The noble gas complexes have been identified via infrared spectroscopy. Quantum chemical calculations of NgBeCO3 and NgBeO (Ng = He, Ne, Ar, Kr, Xe) using ab initio methods and 11



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density functional theory show that the Ng-BeCO3 bonds are slightly longer and weaker than the Ng-BeO bonds. The energy decomposition analysis of the Ng-Be bonds suggests that the attractive interactions come mainly from the Ng→BeCO3 and Ng→BeO σ donation.

ASSOCIATED CONTENT Supporting Information Full references 56 and 57. Table S1 with the

xyz coordinates and energies of the calculated

molecules. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding authors [email protected]; Tel. +86-21-65643532 [email protected]; Tel. +49-6421-2825563 Notes The authors declare no competing financial interest.

ACKNOWLEDGEMENTS The work at Marburg was financially supported by the Deutsche Forschungsgemeinschaft. DMA acknowledges a postdoctoral fellowship from the DAAD (Deutscher Akademischer Austauschdienst). The work at Fudan was financially supported by the National Natural Science Foundation (Grant No. 21433005 and 21173053), Ministry of Science and Technology of China (2013CB834603, and 2012YQ220113-3) and the Committee of Science and Technology of Shanghai (13XD1400800).

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References 1. Laszlo, P.; Schrobilgen, G., One or Several Pioneers - the Discovery of Noble-gas Compounds. Angew. Chem. Int. Ed. Engl. 1988, 27, 479-489. 2. Bartlett, N., Xenon Hexafluoroplatinate(V) Xe+[PtF6]-. Proc. Chem. Soc. 1962, 218. 3. Hoppe, R.; Daehne, W.; Mattauch, H.; Roedder, K., Fluorination of Xenon. Angew. Chem., Int. Ed. Engl. 1962, 1, 599. 4. Claassen, H. H.; Selig, H.; Malm, J. G., Xenon Tetrafluoride. J. Am. Chem. Soc. 1962, 84, 3593. 5. It later turned out that the product of the reaction is actually a mixture of several compounds such as [XeF]+[PtF6]-, [XeF]+[Pt2F11]- and [Xe2F3]+[PtF6]-. Graham, L.; Graudejus, O.; Jha, N. K.; Bartlett, N., Concerning the nature of XePtF6. Coord. Chem. Rev. 2000, 197, 321-334. 6. Fields, P. R.; Stein, L.; H, Z. M. H., Radon Fluoride. J. Am. Chem. Soc. 1962, 84, 4164-4165. 7. Turner, J. J.; Pimentel, G. C., Krypton Fluoride: Preparation by the Matrix Isolation Technique. Science 1963, 140, 974-975. 8. Bartlett, N., The Chemistry of the Noble Gases. Elsevier: New York, 1971. 9. Seppelt, K.; Lentz, D., Novel Developments in Noble Gas Chemistry. Prog. Inorg. Chem. 1982, 29, 167. 10. Christe, K. O., A Renaissance in Noble Gas Chemistry. Angew. Chem., Int. Ed. Engl. 2001, 40, 1419-1421. 11. Liebman, J. F.; Deakyne, C. A., Noble Gas Compounds and Chemistry: A Brief Review of Interrelations and Interactions with Fluorine-Containing Species. J. Fluorine Chem. 2003, 121, 1-8. 12. Frenking, G.; Koch, W.; Deakyne, C. A.; Liebman, J. F.; Bartlett, N., The ArF+ Cation: Is It Stable Enough to be Isolated in a Salt? J. Am. Ceram. Soc. 1989, 111, 31-33. 13. Khriachtchev, L.; Pettersson, M.; Runeberg, N.; Lundell, J.; Räsänen, M., A Stable Argon Compound. Nature 2000, 406, 874-876. 14. Pettersson, M.; Lundell, J.; Räsänen, M., Neutral Rare-Gas Containing Molecules in Solid Matrices II: HXeH, HXeD, and DXeD in Xe. J. Chem. Phys. 1995, 103, 205-210. 15. Pettersson, M.; Nieminen, J.; Khriachtchev, L.; Räsänen, M., The Mechanism of Formation and Infrared-Induced Decomposition of HXeI in Solid Xe. J. Chem. Phys. 1997, 107, 8423-8431. 16. Pettersson, M.; Lundell, J.; Isamieni, L.; Räsänen, M., HXeSH, the First Example of a Xenon-Sulfur Bond. J. Am. Chem. Soc. 1998, 120, 7979-7980. 17. Pettersson, M.; Lundell, J.; Khriachtchev, L.; Räsänen, M., Neutral Rare-Gas Containing Charge-Transfer Molecules in Solid Matrices III HXeCN, HXeNC, and HKrCN in Kr and Xe. J. Chem. Phys. 1998, 109, 618-625. 18. Pettersson, M.; Khriachtchev, L.; Lundell, J.; Räsänen, M., A Chemical Compound Formed from Water and Xenon: HXeOH. J. Am. Chem. Soc. 1999, 121, 11904-11905. 19. Khriachtchev, L.; Räsänen, M.; Gerber, R. B., Noble-Gas Hydrides: New Chemistry at Low Temperatures. Acc. Chem. Res. 2009, 42, 183-191. 13



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20. Perutz, N. R.; Turner, J. J., Photochemistry of Group-6 Hexacarbonyls in Low-Temperature Matrices. 3. Interaction of Pentacarbonyls with Noble-Gases and Other Matrices. J. Am. Chem. Soc. 1975, 97, 4791. 21. Burdett, J. K.; Grzybowsky, J. M.; Perutz, R. N.; Poliakoff, M.; Turner, J. J.; Turner, R. F., Photolysis and Spectroscopy with Polarized-Light - Key to Photochemistry of Cr(CO)5 and Related Species. Inorg. Chem. 1978, 17, 147. 22. Turner, J. J.; Burdett, J. K.; Perutz, R. N.; Poliakoff, M., Matrix Photochemistry of Metal-carbonyls. Pure Appl. Chem. 1977, 49, 271. 23. Wells, J. R.; Weitz, E., Rare-Gas Metal-Carbonyl-Complexes - Bonding of Rare-Gas Atoms to the Group-VI Pentacarbonyls. J. Am. Chem. Soc. 1992, 114, 2783-2787. 24. Weiller, B. H., Metal-Carbonyl-Complexes with Xenon and Krypton – IR Spectra, Co-substitution Kinetics, and Bond-Energies. J. Am. Chem. Soc. 1992, 114, 10910-10915. 25. Ehlers, A. W.; Frenking, G.; Baerends, E. J., Structure and Bonding of the Noble Gas-Metal Carbonyl Complexes M(CO)5-Ng (M = Cr, Mo, W and Ng = Ar, Kr, Xe). Organometallics 1997, 16, 4896-4902. 26. Koch, W.; Collins, J. R.; Frenking, G., Are there Neutral Helium Compounds which are Stable in their Ground State? A Theoretical Investigation of HeBCH and HeBeO. Chem. Phys. Lett. 1986, 132, 330-333. 27. Koch, W.; Frenking, G.; Gauss, J.; Cremer, D.; Collins, J. R., Helium Chemistry: Theoretical Predictions and Experimental Challenge. J. Am. Chem. Soc. 1987, 109, 5917-5934. 28. Frenking, G.; Gauss, W. J.; Cremer, D., Stabilities and Nature of the Attractive Interactions in HeBeO, NeBeO, and ArBeO and a Comparison with Analogs NgLiF, NgBN, and NgLiH (NG = He, Ar): A Theoretical Investigation. J. Am. Chem. Soc. 1988, 110, 8007-8016. 29. Frenking, G.; Koch, W.; Reichel, F.; Cremer, D., Light Noble Gas Chemistry: Structures, Stabilities and Bonding of Helium, Neon and Argon Compounds. J. Am. Chem. Soc. 1990, 112, 4240-4256. 30. Veldkamp, A.; Frenking, G., Structures and Bond Energies of the Noble Gas Complexes NgBeO (Ng = Ar, Kr, Xe). Chem. Phys. Lett. 1994, 226, 11-16. 31. For reviews on the chemistry of the light nobel gas elements see: Jørgensen, C. K.; G., F., Historical, Spectroscopic and Chemical Comparison of Noble Gases. Structure and Bonding 1990, 73, 1-16. 32. Frenking, G.; Cremer, D., The Chemistry of the Noble Gas Elements Helium, Neon, and Argon-Experimental Facts and Theoretical Predictions. Structure and Bonding 1990, 73, 17-95. 33. Thompson, C. A.; Andrews, L., Noble Gas Complexes with BeO: Infrared Spectra of Ng-BeO (Ng = Ar, Kr, Xe). J. Am. Chem. Soc. 1994, 116, 423-424. 34. Andrews, L.; Tague, T. J., Reactions of Pulsed-Laser Evaporated Be Atoms with CO2-Infrared Spectra of OCBeO and COBeO in Solid Argon. J. Am. Chem. Soc. 1994, 116, 6856-6859. 35. Frenking, G.; Koch, W.; Collins, J. R., Fixation of Nitrogen and Carbon Monoxide by Beryllium Oxide: Theoretical Investigation of the Structures and Stabilities of 14


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NNBeO, OCBeO and COBeO. J. Chem. Soc., Chem. Commun. 1988, 17, 1147-1148. 36. Frenking, G.; Dapprich, S.; Köhler, K. F.; Koch, W.; Collins, J. R., Structure and Bonding of the Remarkable Donor-Acceptor complexes XBeO (X = NH3, NMe3, CO, N2, C2H2, C2H4, H2, H2CO, O2). Mol. Phys. 1996, 89, 1245-1263. 37. A discussion of some molecules which are isoelectronic with OCBeO such as OCCO2+ has been presented in Pyykkö, P.; Runeberg, N., Ab Initio Studies of Bonding Trends. Part 8. The 26-electron A≡B−C≡Dn and the 30-electron A=B=C=Dn Systems. J. Mol. Struc. (Theochem) 1991, 243, 266-277. 38. Aschi, M.; Grandinetti, F., FBeNg+ (Ng = He, Ne, Ar): Suitable Cations for Salts of the Lightest Noble Gases? Angew. Chem, Int. Ed. 2000, 39, 1690-1692. 39. Antoniotti, P.; Bronzolino, N.; Grandinetti, F., Stable Compounds of the Lightest Noble Gases: A Computational Investigation of RnBeNg (Ng = He, Ne, Ar). J. Phys. Chem. A 2003, 107, 2974-2980. 40. Borocci, S.; Bronzolino, N.; Grandinetti, F., SBeNg, SBNg+, and SCNg2+ Complexes (Ng = He, Ne, Ar): A Computational Investigation on the Structure and Stability. Chem. Phys. Lett. 2004, 384, 25-29. 41. Borocci, S.; Bronzolino, N.; Grandinetti, F., From OBeHe to H3BOBeHe: Enhancing the Stability of a Neutral Helium Compound. Chem. Phys. Lett. 2005, 406, 179-183. 42. Borocci, S.; Bronzolino, N.; Grandinetti, F., Neutral Helium Compounds: Theoretical Evidence for a Large Class of Polynuclear Complexes. Chem. Eur. J. 2006, 12, 5033-5042. 43. Wang, Q.; Wang, X., Infrared Spectra of NgBeS (Ng = Ne, Ar, Kr, Xe) and BeS2 in Noble-Gas Matrices. J. Phys. Chem. A 2013, 117, 1508-1513. 44. Chen, M. H.; Zhang, Q. N.; Zhou, M. F.; Andrada, D. M.; Frenking, G., Carbon Monoxide Bonding With BeO and BeCO3: Surprisingly High CO Stretching Frequency of OCBeCO3. In print: Angew. Chem, Int. Ed. 2014. 45. Zhou, M. F.; Andrews, L.; Bauschlicher, C. W., Jr., Spectroscopic and Theoretical Investigations of Vibrational Frequencies in Binary Unsaturated Transition-Metal Carbonyl Cations, Neutrals, and Anions. Chem. Rev. 2001, 101, 1931-1961. 46. Wang, G. J.; Zhou, M. F., Probing the Intermediates in the MO + CH4 M + CH3OH Reactions by Matrix Isolation Infrared Spectroscopy. Int. Rev. Phys. Chem. 2008, 27, 1-25. 47. Zhao, Y.; Truhlar, D. G., The M06 Suite of Density Functionals for Main Group Thermochemistry, Thermochemical Kinetics, Noncovalent Interactions, Excited States, and ]Transition Elements: Two New Functionals and Systematic Testing of Four M06-Class Functionals and 12 Other Functionals. Theor. Chem. Acc. 2008, 120, 215-241. 48. Weigend, F.; Ahlrichs, R., Balanced Basis Sets of Split Valence, Triple Zeta Valence and Quadruple Zeta Valence Quality for H to Rn: Design and Assessment of Accuracy. Phys. Chem. Chem. Phys. 2005, 7, 3297-3305. 49. Binkley, J. S.; Pople, J. A., Møller-Plesset Theory for Atomic Ground-State Energies. Int. J. Quantum Chem. 1975, 9, 229-236. 50. Møller, C.; Plesset, M. S., Note on an Approximation Treatment for Many-electron Systems. Physical Review 1934, 46, 618-622. 15



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51. Dunning Jr, T. H., Gaussian Basis Sets for Use in Correlated Molecular Calculations. I. The Atoms Boron Through Neon and Hydrogen. J. Chem. Phys. 1989, 90, 1007-1023. 52. Woon, D. E.; Dunning Jr, T. H., Gaussian Basis Sets for Use in Correlated Molecular Calculations. IV. Calculation of Static Electrical Response Properties. J. Chem. Phys. 1994, 100, 2975-2988. 53. Purvis III, G. D.; Bartlett, R. J., A Full Coupled-Cluster Singles and Doubles Model - the Inclusion of Disconnected Triples. J. Chem. Phys. 1982, 76, 1910-1918. 54. Peng, C. Y.; Ayala, P. Y.; Schlegel, H. B.; Frisch, M. J., Using Redundant Internal Coordinates to Optimize Equilibrium Geometries and Transition States. J. Comput. Chem. 1996, 17, 49-56. 55. McIver, J. W.; Komornic, A., Structure of Transition-States in Organic Reactions General Theory and an Application to Cyclobutene-Butadiene Isomerization Using a Semiempirical Molecular-Orbital Method. J. Am. Chem. Soc. 1972, 94, 2625-2633. 56. Frisch, M.J.; Trucks, G.W.; Schlegel, H.B.; Scuseria G.E.; Robb, M.A.; Cheeseman, J.R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G.A. et al. Gaussian 09, Revision C.01. Gaussian, Inc.: Wallingford CT, 2009. 57. Werner, H.-J.; Knowles, P. J.; Knizia, G.; Manby, F. R.; Schütz, M.; Celani, P.; Korona, T.; Lindh, R.; Mitrushenkov, A.; Rauhut, G. et al. MOLPRO, 2012.1; http://www.molpro.net, 2012. 58. Werner, H. J.; Knowles, P. J.; Knizia, G.; Manby, F. R.; Schütz, M., Molpro: A general-purpose quantum chemistry program package. WIREs Comput. Mol. Sci. 2012, 2, 242-253. 59. Becke, A. D., Density-Functional Exchange-Energy Approximation with Correct Asymptotic-Behavior. Phys. Rev. A 1988, 38, 3098-3100. 60. Perdew, J. P., erdew, J. P. Density-Functional Approximation for the Correlation-Energy of the Inhomogeneous Electron-Gas. Phys. Rev. B 1986, 33, 8822-8824. 61. Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H., A Consistent and Accurate Ab Initio Parametrization of Density Functional Dispersion Correction (DFT-D) for the 94 Elements H-Pu. J. Chem. Phys. 2010, 132, 154104-154119. 62. Snijders, J. G.; Baerends, E. J.; Vernooijs, P., Roothaan-Hartree-Fock-Slater Atomic Wave Functions: Single-Zeta, Double-Zeta, and Extended Slater-Type Basis Sets for 87Fr-103Lr. At. Nucl. Data Tables 1982, 26, 483-509. 63. Krijn, J.; Baerends, E. J., Fit Functions in the HFS-Method. Free University of Amsterdam: The Netherlands, 1984. 64. Te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J.; Fonseca Guerra, C.; Van Gisbergen, S. J. A.; Snijders, J. G.; Ziegler, T., Chemistry with ADF. J. Comput. Chem. 2001, 22, 931-967. 65. Morokuma, K., Molecular Orbital Studies of Hydrogen Bonds. 3. C=O H-O Hydrogen Bond in H2CO•••H2O and H2CO•••2H2O. J. Chem. Phys. 1971, 55, 1236-1244. 66. Ziegler, T.; Rauk, A., CO, CS, N2, PF3, and CNCH3 as -Donors and π-Acceptors – Theoretical Study by the Hartree-Fock-Slater Transition-State Method. Inorg. Chem. 1979, 18, 1755-1759. 16


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67. Bickelhaupt, F. M.; Baerends, E. J., Kohn-Sham Density Functional Theory: Predicting and Understanding Chemistry. In Reviews in Computational Chemistry, 2000; Vol. 15, pp 1-86. 68. Frenking, G.; Wichmann, K.; Fröhlich, N.; Loschen, C.; Lein, M.; Frunzke, J.; Rayón, V. M., Towards a Rigorously Defined Quantum Chemical Analysis of the Chemical Bond in Donor-Acceptor Complexes. Coord. Chem. Rev. 2003, 238-239, 55-82. 69. Lein, M.; Frenking, G., The Nature of the Chemical Bond in the Light of an Energy Decomposition Analysis. In Theory and Applicactions of Computational Chemistry: The First 40 Years., Dykstra, C. E.; Frenking, G.; Kim, K. S.; Scuseria, G. E., Eds. Elsevier: Amsterdam, 2005; pp 291-372. 70. Krapp, A.; Bickelhaupt, F. M.; Frenking, G., Orbital Overlap and Chemical Bonding. Chem. Eur. J. 2006, 12, 9196-9216. 71. Frenking, G.; Bickelhaupt, F. M., The EDA Perspective of Chemical Bonding. In The Chemical Bond 1. Fundamental Ascpects of Chemical Bonding, Frenking, G.; Shaik, S., Eds. Wiley-VCH: Weinheim, 2014; pp 121-158. 72. Mitoraj, M. P.; Michalak, A.; Ziegler, T., A Combined Charge and Energy Decomposition Scheme for Bond Analysis. J. Chem. Theory Comput. 2009, 5, 962-975. 73. Mitoraj, M.; Michalak, A., Donor-Acceptor Properties of Ligands from the Natural Orbitals for Chemical Valence. Organometallics 2007, 26, 6576-6580. 74. Mitoraj, M.; Michalak, A., Applications of Natural Orbitals for Chemical Valence in a Description of Bonding in Conjugated Molecules. J. Mol. Modeling 2008, 14, 681-687. 75. For recent examples see: Devarajan, D.; Frenking, G., Are they Linear, Bent or Cyclic? Quantum Chemical Investigation of the Heavier Group-14 and Group-15 Homologues of HCN and HNC. Chem. Asian J. 2012, 7, 1296-1311. 76. Nguyen, T., A. N.; Frenking, G., Transition Metal Complexes of Tetrylones [(CO)5W-{E(PPh3)2}] and Tetrylenes (CO)5W-NHE] (E = C – Pb): A Theoretical Study. Chem. Eur. J. 2012, 18, 12733-12748. 77. Holzmann, N.; Dange, C.; Jones, C.; Frenking, G., Dinitrogen as Double Lewis Acid: Structure and Bonding of Triphenylphosphinazine N2(PPh3)2. Angew. Chem, Int. Ed. 2013, 2, 3004-3008. 78. Mousavi, M.; Frenking, G., Bonding Analysis and Theoretical Studies of the Trimethylenemethane (TMM) Complexes (η6-C6H6)M-TMM (M = Fe, Ru ,Os), (η5-C5H5)M-TMM (M = Co, Rh, Ir) and (η4-C4H4)M-TMM (M = Ni, Pd, Pt). Organometallics 2013, 32, 1743-1755. 79. Das, A.; Dash, C.; A., C. M.; Yousufuddin, M.; Frenking, G.; R., D. H. V., Tris(alkyne) and Bis(alkyne) Complexes of Coinage Metals: Synthesis and Characterization of (Cyclooctyne)3M+ (M = Cu, Ag) and (Cyclooctyne)2Au+ and Coinage Metal (M = Cu, Ag, Au) Family Group Trends. Organometallics 2013, 32, 3135-3144. 80. Celik, M. A.; Frenking, G.; Neumüller, B.; Petz, W., Exploiting the Twofold Donor Ability of Carbodiphosphoranes: Theoretical Studies of [(PPh3)2C-EH2]q (Eq = Be, B+, C2+, N3+, O4+) and Synthesis of the Dication [(Ph3P)2C=CH2]2+. ChemPlusChem. 2013, 78, 1024-1032. 17



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81. Nguyen, T., A. N. ; Frenking, G., Structure and Bonding of Tetrylone Complexes [(CO)4W{E(PPh3)2}] (E = C - Pb). Mol. Phys. 2013, 111, 2640-2646. 82. Hermann, M.; Goedecke, C.; Jones, C.; Frenking, G., Reaction Pathways for Addition of H2 to Amido-Ditetrylynes R2N-EE-NR2 (E = Si, Ge, Sn): A Theoretical Study. Organometallics 2013, 32, 6666-6673. 83. Thompson, W. E.; Jacox, M. E., The Vibrational Spectra of Molecular-Ions Isolated in Solid Neon. 7. CO+, C2O2+, and C2O2-. J. Chem. Phys. 1991, 95, 735-745. 84. Thompson, W. E.; Jacox, M. E., The Vibrational Spectra of Molecular Ions Isolated in Solid Neon 2. O4+ and O4-. J. Chem. Phys. 1989, 91, 3826-3837. 85. Andrews, L.; Tague, T. J., Jr.; Kushto, G. P.; Davy, R. D., Infrared Spectra of Beryllium Carbonyls from Reactions of Beryllium Atoms with Carbon Monoxide in Solid Argon. Inorg. Chem. 1995, 34, 2952-2961. 86. Thompson, C. A.; Andrews, L., Reactions of Laser-Ablated Be Atoms with O2-Infrared Spectra of Beryllium Oxides in Solid Argon. J. Chem. Phys. 1994, 100, 8689-8699. 87. Zhou, Z. J.; Li, Y. Z.; Zhuang, J.; Wang, G. J.; Chen, M. H.; Zhao, Y. Y.; Zheng, X. M.; Zhou, M. F., Formation and Characterization of Two Interconvertible Side-On and End-On Bonded Beryllium Ozonide Complexes. J. Phys. Chem. A 2011, 115, 9947-9953. 88. Shorter but weaker bonds have been reported in: Pidun, U.; Frenking, G., Complexes of Transition Metals in High and Low Oxidation States with Side-on-Bonded π-Ligands. Organometallics 1995, 14, 5325-5336. 89. Pidun, U.; Frenking, G., The Bonding of Acetylene and Ethylene in High-Valent and Low-Valent Transition Metal Compounds. J. Organomet. Chem. 1996, 525, 269-278. 90. Fischer, R. A.; Schulte, M. M.; Weiß, J.; Zsolnai, L.; Jacobi, A.; Huttner, G.; Frenking, G.; Boehme, C.; Vyboishchikov, S. F., Transition Metal Coordinated Al(X)L2 and Ga(X)L2 Complexes. J. Am. Chem. Soc. 1998, 120, 1237-1248. 91. Frenking, G.; Wichmann, K.; Fröhlich, N.; Grobe, J.; Golla, W.; Le, V. D.; Krebs, B.; Läge, M., Nature of the Metal-Ligand Bond in M(CO)5PX3 Complexes (M = Cr, Mo, W; X = H, Me, F, Cl): Synthesis, Molecular Structure, and Quantum Chemical Calculations. Organometallics 2002, 21, 2921-2930. 92. Celik, M. A.; Sure, R.; Klein, S.; Kinjo, R.; Bertrand, G.; Frenking, G., Borylene Complexes (BH)L2 and Nitrogen Cation Complexes (N+)L2-Isoelectronic Homologues of Carbones CL2. Chem. Eur. J. 2012, 18, 5676-5692. 93. Huber, K. P.; Herzberg, G., Molecular Spectra and Molecular Structure IV: Constants of Diatomic Molecules. Van Nostrand Reinhold: New York, 1979.

18


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Page 19 of 32

0.04

NeBeCO3

0.03

Absorbance

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Be2O2

NeBeCO3

NeBeCO3

Be2O2 (c)

0.02

BeBeCO

OCBeBeCO (b)

0.01

-

Be(CO)3

O4

+ BeO2

Be(CO)2 (a)

0.00 2000

1900

1200

1100

1000

900

800

700

-1

Wavenumber / cm

Figure 1. Infrared spectra in the 2000-1800 and 1225-700 cm-1 regions from co-deposition of laser-evaporated Be atoms with 0.05% O2 + 0.025% CO in neon. (a) after 30 min of sample deposition at 4 K, (b) after 12 K annealing, and (c) after 15 min of UV-visible light (250 < λ < 580 nm) irradiation.

19



0.100 (e)

0.075 (d)

Absorbance

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 20 of 32

(c)

0.050

13

NeBe CO3

13

13

NeBe CO3

NeBe CO3

(b)

0.025

NeBeCO3 NeBeCO3 Be2O2

0.000 1900 1850

1200

1100

Be2O2

NeBeCO3 (a)

1000

900

800

700

-1

Wavenumber / cm

Figure 2. Infrared spectra in the 1900-1800 and 1220-700 cm-1 regions from co-deposition of laser-evaporated Be atoms with isotopic-labeled O2/CO mixtures in excess neon (Spectra were taken after 15 min of UV-visible light (250 < λ < 580 nm) irradiation). (a) 0.05% 16O2 + 0.025% 12 16

C O, (b) 0.05% 16O2 + 0.025% 13C16O, (c) 0.05% 16O2 + 0.025% 12C16O + 0.025% 13C16O, (d)

0.05% 16O2+ 0.025% 12C18O, (e) 0.05% 16O2 + 0.025% 12C16O + 0.025% 12C18O .

20


Page 21 of 32

0.0500

18

NeBeC O3

NeBeCO3 (d)

0.0375

Absorbance

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(c)

0.0250 (b) NeBeCO3

0.0125 Be2O2

0.0000 1900 1850

NeBeCO3

Be2O2

NeBeCO3

(a)

1200

1100

1000

900

800

700

-1

Wavenumber / cm

Figure 3. Infrared spectra in the 1900-1800 and 1220-700 cm-1 regions from co-deposition of laser-evaporated Be atoms with isotopic-labeled O2/CO mixtures in excess neon (Spectra were taken after 15 min of UV-visible light (250 < λ < 580 nm) irradiation). (a) 0.05% 16O2 + 0.025% 12 16

C O, (b) 0.05% 18O2 + 0.025% 12C16O, (c) 0.025%

18

16

O2 + 0.025% 18O2 + 0.025% (d) 0.05%

O2+ 0.025% 12C18O.

21



0.04 XeBeCO3

XeBeCO3

(d)

0.03

Absorbance

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 22 of 32

KrBeCO3

KrBeCO3

(c)

0.02 ArBeCO3

ArBeCO3 (b)

0.01

NeBeCO3

NeBeCO3

(a)

0.00 1875

1850

1225

1200

1175

-1

Wavenumber / cm

Figure 4. Infrared spectra in the 1880-1835 and 1225-1170 cm-1 regions from co-deposition of laser-evaporated Be atoms with 0.05% 16O2 + 0.025% 12C16O in neon doped with heavier noble gases (Spectra were taken after 15 min of UV-visible light (250 < λ < 580 nm) irradiation). (a) Ne, (b) 0.025% Ar/Ne, (c) 0.025% Kr/Ne, and (d) 0.025% Xe/Ne.

22


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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


α 96.7 (97.5) [97.4]

1.468 (1.478) [1.476]

1.318 (1.354) [1.344]

α

β

β γ 79.3 104.8 (78.7) (105.2) [78.9] [104.9] 1.179 (1.188) [1.188]

γ

1.384 (1.399) [1.398] 1.315 (1.346) [1.336]

1.317 (1.347) [1.337]

1.519 (1.521) [1.522]

1.319 (1.347) [1.338]

1.794 (1.796) [1.789]

2.069 (2.076) [2.071]

1.320 (1.348) [1.339]

1.321 (1.349) [1.341]

2.221 (2.212) [2.209] 1.472 (1.483) [1.480] 1.609 (1.611) [1.606] α 95.8 (96.5) [96.3]

αβ

2.408 (2.389) [2.385] 1.474 (1.484) [1.481]

1.180 (1.189) [1.188]

α

γ

1.842 (1.813) [1.799] α β γ 95.7 79.8 104.7 (96.3) (79.4) (104.9) [96.2] [79.6] [104.6]

1.381 (1.395) [1.394]

β γ 79.8 104.6 (79.3) (104.9) [79.5] [104.6]

1.484 (1.493) [1.491] 2.269 (2.260) [2.255] α 94.4 (95.2) [95.0]

β

αβ

β γ 80.4 104.7 (79.9) (105.0) [80.2] [104.7]

γ

1.481 (1.491) [1.488]

1.180 (1.189) [1.189]

α 2.110 (2.111) [2.107] α β γ 94.8 80.3 104.7 (95.4) (79.8) (104.9) [95.3] [80.0] [104.7]

1.380 (1.394) [1.393]

1.486 (1.496) [1.494]

1.183 (1.191) [1.191]

γ

2.459 (2.445) [2.443]

1.375 (1.390) [1.388]

β

α 94.2 (94.9) [94.7]

αβ

β γ 80.5 104.9 (80.1) (105.0) [80.3] [104.8]

γ

1.182 (1.191) [1.191]

1.376 (1.391) [1.389]

1.183 (1.192) [1.192]

γ 1.374 (1.388) [1.386]

Figure 5. Optimized geometries at M06-2X/def2-TZVPP, MP2/cc-pVTZ (in parenthesis) and CCSD(T)/cc-pVTZ (in brackets). The bond lengths and angles are in [Å] and [°], respectively.

23



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Page 24 of 32

Table 1. Experimental Infrared Absorptions (cm-1) of Isotopic-Labelled NeBeCO3 in Solid Neon. All values in cm-1.

mode

16

O2+12C16O

16

O2+13C16O

16

O2+12C18O

18

O2+12C16O

18

O2+12C18O

CO str.

1863.6

1819.5

1856.4, 1832.6

1858.6, 1831.0

1829.3

CO2 &BeO2 asym. str.

1202.6

1190.8

1021.9, 1192.8

1192.0, 1179.8

1178.9

BeO2 sym. str.

1107.6

1107.2

1107.1, 1094.9

1095.0, 1084.0

1084.0

CO2 sym. str.

867.3

863.1

855.5, 854.2

841.4, 839.0

825.1

CO3 out-of-plane bend.

795.3

772.2

791.8(broad)

788.5(broad)

785.0

CO3 in-plane bend.

779.9

765.8

779.7, 774.1

773.9, 770.8

770.0

BeO2 & CO2 scissor

745.2

743.5

737.0, 734.2

726.9, 722.5

716.1

24


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Table 2. Infrared Absorptions of NgBeCO3 (Ng=Ne-Xe) in Solid Neon. All values in cm-1. Assignment

NeBeCO3

ArBeCO3

KrBeCO3

XeBeCO3

CO str.

1863.6

1854.8

1851.2

1846.3

CO2 & BeO2 asym. str.

1202.6

1192.3

1187.2

1179.9

BeO2 sym. str.

1107.6

1105.5

1101.1

1091.5

CO2 sym. str.

867.3

875.8

877.0

877.2

CO3 out-of-plane bend.

795.3

799.8

800.8

802.0

CO3 in-plane bend.

779.5

786.8

786.8

785.7

BeO2 & CO2 scissor

745.2

752.7

752.7

750.8

25



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Table 3. Calculated and experimental vibrational frequencies (in italics) of normal modes ν (in cm-1) at M06-2X/def2-TZVPP. Symmetry assignments and intensities (in km/mol) are given in parenthesis. The Ng-BeY (Y = O, CO3) stretching mode is given in bold. The experimental values are from this study except when otherwise noted. Compound

Frequencies

BeO

ν1: 1592, 1487b (σ, 55)

HeBeO

ν1: 1656 (σ, 115); ν2: 514 (σ, 0); ν3a: 211 (π, 55)

HeBeCO3

ν1: 1967 (a1, 522); ν2: 1272 (b2, 479); ν3: 1165 (a1, 193); ν4: 924 (a1, 201); ν5: 826 (b1, 39); ν6: 823 (b2, 48); ν7: 766 (a1, 68); ν8: 598 (b2, 1); ν9: 347 (a1, 2); ν10: 325 (b1, 70); ν11: 154 (b2, 0); ν12: 102 (b1, 1)

NeBeO

ν1: 1631 (σ, 130); ν2: 226 (σ, 2); ν3a: 159 (π, 102)

NeBeCO3

ν1: 1964,1864 (a1, 520); ν2: 1267, 1203 (b2, 482); ν3: 1160,1108 (a1, 207); ν4: 926, 867 (a1, 211); ν5: 826, 795 (b1, 39); ν6: 821, 780 (b2, 45); ν7: 765, 745 (a1, 77); ν8: 598 (b2, 1); ν9: 325 (b1, 70); ν10: 178 (a1, 1); ν11: 98 (b2, 6); ν12: 70 (b1, 10)

ArBeO

ν1: 1637, 1526c (σ, 201); ν2: 277 (σ, 2); ν3a: 177 (π, 76)

ArBeCO3

ν1: 1956, 1855 (a1, 568); ν2: 1260, 1192 (b2, 437); ν3: 1160, 1106 (a1, 300); ν4: 935,876 (a1, 255); ν5: 832, 800 (b1, 37); ν6: 831,787 (b2, 37); ν7: 774, 753 (a1, 82); ν8: 600 (b2, 1); ν9: 338 (b1, 51); ν10: 200 (a1, 1); ν11: 108 (b2, 4); ν12: 86 (b1, 6).

KrBeO

ν1: 1626, 1522c

(σ, 207); ν2: 223 (σ, 1); ν3a: 161 (π, 70)

KrBeCO3

ν1: 1951, 1851 (a1, 590); ν2: 1254,1187 (b2, 420); ν3: 1156, 1101 (a1, 316); ν4: 939,877 (a1, 274); ν5: 832, 801 (b1, 36); ν6: 831, 787 (b2, 32); ν7: 776, 753 (a1, 81); ν8: 601 (b2, 0); ν9: 338 (b1, 45); ν10: 169 (a1, 0); ν11: 96 (b2, 4); ν12: 80 (b1, 7) 1517c (σ, 214); ν2: 215 (σ, 0); ν3a: 148 (π, 63)

XeBeO

ν1: 1620,

XeBeCO3

ν1: 1948, 1846 (a1, 619); ν2: 1249, 1180 (b2, 400); ν3: 1149, 1092 (a1, 335); ν4: 940, 877 (a1, 299); ν5: 833, 802 (b1, 35); ν6: 830, 786 (b2, 29); ν7: 774, 751 (a1, 90); ν8: 600 (b2, 0); ν9: 330 (b1, 37); ν10: 150 (a1, 0); ν11: 80 (b2, 4); ν12: 67 (b1, 7)

a

Degenerate mode. bRef. 93. cRef. 34. 26


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Table 4. Calculated and experimental vibrational frequencies (in italics) of normal modes ν (in cm-1) at MP2/cc-pVTZ. Symmetry assignments and intensities (in km/mol) are given in parenthesis. The Ng-BeY (Y = O, CO3) stretching mode is given in bold. The experimental values are from this study except when otherwise noted. Compound

Frequencies

BeO

ν1: 1406, 1487b (σ, 11)

HeBeO

ν1: 1513 (σ, 6); ν2: 499 (σ, 0); ν3a: 201 (π, 30)

HeBeCO3

ν1: 1912 (a1, 429); ν2: 1231 (b2, 396); ν3: 1127 (a1, 187); ν4: 874 (a1, 182); ν5: 795 (b1, 28); ν6: 775 (b2, 74); ν7: 746 (a1, 71); ν8: 584 (b2, 3); ν9: 363 (a1, 2); ν10: 324 (b1, 72); ν11: 164 (b2, 0); ν12: 101 (b1, 0)

NeBeO

ν1: 1497 (σ, 16); ν2: 257 (σ, 3); ν3a: 166 (π, 68)

NeBeCO3


ArBeO

ν1: 1514, 1526c (σ, 40); ν2: 272 (σ, 3); ν3a: 165 (π, 51)

ArBeCO3


KrBeO

ν1: 1511, 1522c (σ, 44); ν2: 246 (σ, 2); ν3a: 159 (π, 46)

KrBeCO3

ν1: 1901, 1851 (a1, 483); ν2: 1209,1187 (b2, 345); ν3: 1116, 1101 (a1, 311); ν4: 886, 877 (a1, 246); ν5: 801, 801 (b1, 26); ν6: 787, 787 (b2, 57); ν7: 753, 753 (a1, 92); ν8: 587 (b2, 1); ν9: 325 (b1, 47); ν10: 159 (a1, 1); ν11: 92 (b2, 4); ν12: 65 (b1, 6)

XeBeO

ν1: 1507, 1517c (σ, 42); ν2: 236 (σ, 1); ν3a: 155(π, 39)

XeBeCO3


a

Degenerate mode. bRef. 93. cRef. 34. 27



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Page 28 of 32

Table 5. Calculated and experimental vibrational frequencies (in italics) of normal modes ν(in cm-1) at CCSD(T)/cc-pVTZ. Symmetry assignments and intensities (in km/mol) are given in parenthesis. The Ng-BeY (Y = O, CO3) stretching mode is given in bold. The experimental values are from this study except when otherwise noted. Compound

Frequencies

BeO

ν1: 1458, 1487b (σ)

HeBeO

ν1: 1560 (σ); ν2: 498 (σ); ν3a: 188 (π)

HeBeCO3

ν1: 1916 (a1); ν2: 1243 (b2); ν3: 1136 (a1); ν4: 878 (a1); ν5: 797 (b1); ν6: 797 (b2); ν7: 753 (a1); ν8: 584 (b2); ν9: 372 (a1); ν10: 326 (b1); ν11: 165 (b2); ν12: 106 (b1)

NeBeO

ν1: 1545 (σ); ν2: 259 (σ); ν3a: 158 (π)

NeBeCO3

ν1: 1914,1864 (a1); ν2: 1240, 1203 (b2); ν3: 1136, 1108 (a1); ν4: 881, 867 (a1); ν5: 800, 795 (b1); ν6: 798, 780 (b2); ν7: 755, 745 (a1); ν8: 584 (b2); ν9: 326 (b1); ν10: 211 (a1); ν11: 107 (b2); ν12: 72 (b1)

ArBeO

ν1: 1556, 1526c (σ); ν2: 276 (σ); ν3a: 159 (π)

ArBeCO3

ν1: 1906, 1855 (a1); ν2: 1228, 1192 (b2); ν3: 1129, 1106 (a1); ν4: 889, 876 (a1); ν5: 808, 800 (b2); ν6: 802, 787 (b1); ν7: 760, 753 (a1); ν8: 587 (b2); ν9: 329 (b1); ν10: 198 (a1); ν11: 100 (b2); ν12: 69 (b1) (σ); ν2: 250 (σ); ν3a: 156 (π)

KrBeO

ν1: 1552, 1522c

KrBeCO3

ν1: 1903, 1851 (a1); ν2: 1222, 1187 (b2); ν3: 1124, 1101 (a1); ν4: 891, 877 (a1); ν5: 808, 801 (b2); ν6: 804, 787 (b1); ν7: 760, 753 (a1); ν8: 587 (b2); ν9: 329 (a1); ν10: 162 (b1); ν11: 95 (b2); ν12: 68 (b1)

XeBeO

ν1: 1547, 1517c (σ); ν2: 239.0 (σ); ν3a: 151 (π)

XeBeCO3

ν1: 1899, 1846 (a1); ν2: 1215, 1180 (b2); ν3: 1117, 1092 (a1); ν4: 893, 877 (a1); ν5: 807, 802 (b2); ν6: 805, 786 (b1); ν7: 759, 751 (a1); ν8: 587 (b2); ν9: 326 (b1); ν10: 146 (a1); ν11: 87 (b2); ν12: 64 (b1)

a

Degenerate mode. bRef. 93. cRef. 34.

28


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Table 6. Shift of the experimental and calculated IR frequencies of NgBeCO3 (Ng = Ar Xe) in solid neon with respect to NeBeCO3.

CO

CO2 & BeO2

BeO2

CO3

BeO2 & CO2

stretch

asym. str.

sym. str.

out-of-plane

scissor

bend. ArBeCO3 exper.

-9

-10

-2

+5

+8

M06-2X/def2-TZVPP

-8

-7

+0

+6

+9

MP2/cc-pVTZ

-7

-12

-5

+4

+6

CCSD(T)/cc-pVTZ

-8

-12

-7

+8

+5

KrBeCO3 exper.

-12

-15

-7

+6

+8

M06-2X/def2-TZVPP

-13

-13

-4

+6

+11

MP2/cc-pVTZ

-9

-18

-11

+5

+5

CCSD(T)/cc-pVTZ

-11

-18

-12

+8

+4

XeBeCO3 exper.

-17

-22

-16

+7

+6

M06-2X/def2-TZVPP

-16

-18

-11

+7

+9

MP2/cc-pVTZ

-13

-25

-17

+7

+5

CCSD(T)/cc-pVTZ

-15

-25

-19

+7

+4

29



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Page 30 of 32

Table 7. Calculated dissociation energies of the Ng-BeY bonds De and D0 (in kcal/mol) at different levels of theory. M06-2X/def2-TZVPP

MP2/cc-pVTZ

CCSD(T)/cc-pVTZ

CCSD(T)/CBS// CCSD(T)/cc-pVTZ

NgBeY

De

D0

De

D0

De

D0

De

D0

HeBeO

6.4

5.0

5.1

3.7

4.9

3.5

5.1

3.7

HeBeCO3

4.1

3.1

3.2

2.2

3.4

2.4

3.6

2.5

NeBeO

6.0

5.2

6.1

5.1

6.0

5.1

4.9

4.0

NeBeCO3

5.0

4.4

5.9

5.1

6.2

5.4

4.6

3.8

ArBeO

13.3

12.4

11.9

10.9

12.1

11.2

11.9

10.9

ArBeCO3

11.1

10.4

10.6

9.9

10.9

10.2

10.4

9.7

KrBeO

15.6

14.7

14.0

13.1

14.3

13.4

13.5

12.6

KrBeCO3

13.0

12.3

12.1

11.4

12.4

11.8

11.7

11.1

XeBeO

17.4

16.6

16.5

15.6

16.9

16.0

15.9

15.0

XeBeCO3

14.3

13.8

13.8

13.2

14.2

13.6

13.5

12.9

30


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Table 8. Energy decomposition analysis (EDA-NOCV) at the BP86-D3/TZ2P+//CCSD(T)/cc-pVTZ level of theory for the Ng-Be bond in the Ng-BeO and Ng-BeCO3 (Ng = He, Ne, Ar, Kr, Xe) complexes. The interacting fragmentsa are Ng + BeO and Ng + BeCO3, respectively. Energy values are given in kcal/mol. He-BeO ∆Eint ∆EPauli ∆Edispa ∆Eelstata ∆Eorba ∆Eorb(a1)b σ ∆Eorb(b1)b πǁ ∆Eorb(b2)b π┴ ∆Eorb(rest)b ∆Eprep De

-4.7 +8.5 -0.2 (1.5 %) -1.5 (11.3 %) -11.6 (87.2 %) -9.3 (80.2 %) -0.3 (2.5 %) -0.3 (2.5 %) -1.7 (14.7 %) 0.0 4.7

He-BeCO3 -3.1 +7.1 -0.4 (3.9 %) -0.9 (8.8 %) -8.9 (87.3 %) -8.2 (92.1 %) -0.2 (2.2 %) -0.1 (1.1 %) -0.4 (4.5 %) +0.2 2.9

Ne-BeO -4.4 +11.2 -0.2 (1.3 %) -4.2 (26.9 %) -11.2 (71.8 %) -7.8 (69.6 %) -1.3 (11.6 %) -1.3 (11.6 %) -0.8 (7.1 %) 0.0 4.4

Ne-BeCO3 -3.9 +9.5 -0.6 (4.4 %) -2.2 (16.3 %) -10.7 (79.2 %) -7.7 (72.0 %) -1.2 (11.2 %) -1.3 (12.1 %) -0.5 (4.7 %) +0.2 3.7

Ar-BeO -11.4 +16.9 -0.4 (1.4 %) -6.0 (21.2 %) -21.9 (77.4 %) -15.6 (71.2 %) -2.6 (11.9 %) -2.6 (11.9 %) -1.1 (5.0%) 0.0 11.4

Ar-BeCO3

Kr-BeO

-9.7 +13.6 -1.0 (4.3 %) -2.5 (10.7 %) -19.9 (85.0 %) -15.0 (75.4 %) -2.1 (10.6 %) -2.2 (11.1 %) -0.6 (3.0 %) +0.5 9.7

-13.7 +17.9 -0.5 (1.6 %) -6.4 (20.2 %) -24.8 (78.2 %) -18.1 (73.0 %) -2.8 (11.3 %) -2.8 (11.3 %) -1.1 (4.4 %) 0.0 13.7

Kr-BeCO3 -11.8 +13.9 -1.2 (4.7 %) -2.3 (8.9 %) -22.3 (86.4 %) -17.1 (76.7 %) -2.2 (9.9 %) -2.4 (10.8 %) -0.6 (2.7 %) +0.5 11.3

a

The value in parenthesis gives the percentage contribution to the total attractive interactions ∆Eelstat + ∆Eorb + ∆Edisp.

b

The value in parenthesis gives the percentage contribution to the total orbital interactions ∆Eorb. 31


Xe-BeO -16.6 +18.8 -0.5 (5.8 %) -6.8 (8.6 %) -28.1 (79.4 %) -21.3 (75.8 %) -2.9 (10.3 %) -2.9 (10.3 %) -1.0 (3.6 %) 0.0 16.6

Xe-BeCO3 -14.1 +14.2 -1.4 (4.9 %) -2.1 (7.4 %) -24.9 (87.7 %) -19.9 (79.9 %) -2.1 (8.4 %) -2.3 (9.2 %) -0.6 (2.4 %) +0.7 13.4


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Graphical Abstract.

32


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Experimental and Theoretical Studies of the Infrared Spectra and

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