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Gold with +4 and +6 Oxidation States in AuF and AuF Jianyan Lin, Shoutao Zhang, Wei Guan, Guochun Yang, and Yanming Ma

J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b04563 • Publication Date (Web): 12 Jul 2018 Downloaded from http://pubs.acs.org on July 12, 2018

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Journal of the American Chemical Society

Gold with +4 and +6 Oxidation States in AuF4 and AuF6 Jianyan Lin1,‡, Shoutao Zhang1,‡, Wei Guan2, Guochun Yang1,*, and Yanming Ma3,4,5* 1

Centre for Advanced Optoelectronic Functional Materials Research and Key Laboratory for UV Light-Emitting Materials and Technology of Ministry of Education, 2Department of Chemistry, Northeast Normal University, Changchun 130024, China

3

State Key Lab of Superhard Materials, College of Physics, Jilin University, Changchun 130012, China

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International Center of Future Science, Jilin University, Changchun 130012, China

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Innovation Center for Computational Physics Method and Software, College of Physics, Jilin University, Changchun 130012, China

ABSTRACT: An important goal in chemistry is to prepare compounds with unusual oxidation states showing exciting

properties. For gold (Au), the relativistic expansion of its 5d orbitals makes it form high oxidation state compounds. Till thus far, the highest oxidation state of Au known is +5. Here, we propose high pressure as a controllable method for preparing +4 and +6 oxidation states in Au via its reaction with fluorine. First-principles swarm-intelligence structure search identifies two hitherto unknown stoichiometric compounds, AuF4 and AuF6, exhibiting typical molecular crystal character. The high-pressure phase diagram of Au fluorides is rather different from Cu or Ag fluorides, which is indicated by stable chemical compositions and the pressures needed for the synthesis of these compounds. This difference can be associated with the stronger relativistic effects in Au relative to Cu or Ag. Our work represents a significant step forward in a more complete understanding of the oxidation states of Au.

1. INTRODUCTION The formalism of the oxidation state of atoms in compounds is a key concept in chemistry.1,2,3 Finding novel compounds containing elements with unusually high oxidation states allows a deeper understanding of chemical behavior of elements.2,4,5 On the other hand, high oxidation state compounds usually bring new types of bonds with interesting physical and chemical properties.6,7 Thus, the preparation of compounds with unusual oxidation states becomes an attractive topic in chemistry and condensed-matter physics.5,8,9,10 Considering the diverse d electron configurations of transition metal elements, much effort has been made to explore their potential oxidation states.2,11,12 Interestingly, some of the transition metal compounds with high oxidation states serve as catalysts,13 fluorinating agents,14 and oxidants.15 Au is a fascinating element on the periodic table due to its extreme inertness at ambient conditions and considerable chemical activity under certain conditions.16,17,18 The oxidation states of Au, inducing interesting chemical and physical properties in its compounds, have become

one of the most active areas in both basic and applied research.10,19,20,21,22 Up to now, five different oxidation states of Au (-1, +1, +2, +3, and +5)20,21 have been confirmed in its compounds. In particular, Au compounds have shown a broad application as catalysts.23,24,25,26,27 For instance, Au(I) compounds have been widely used for the activation of C-C multiple bonds,28,29,30,31,32 and inorganic Au(III) compounds participate in intramolecular cyclization reactions producing heterocycles.33,34,35,36 On the other hand, the reluctance of Au(I) compounds to undergo oxidation addition becomes an obstacle for the development of gold-catalyzed cross-coupling reaction,37,38,39 which recently has been overcome by the use of diazonium salts instead of organic halides.40,41,42,43 In more detail, the preparation of stable and catalytically active organometallic Au(III) compounds under mild conditions is rather difficult due to the high redox potential of Au(III),44,45,46,47 but becomes possible for example with hypervalent iodine reagents.48 Alternatively, the intramolecular oxidative addition of aryl halides to Au(I) compounds has been successfully achieved through ligand regulation strategy.49 Subsequently, several Au(III)

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compounds have been found showing high activity as catalytic intermediates,22,50,51,52 complementing the library of Au(I)-catalytic reactions.53,54 Therefore, it is highly interesting to explore Au compounds with high oxidation states, allowing for a deeper understanding of its catalytic cycle, and extending its potential applications in material science.22,51,55 All these diverse oxidation states and distinct properties of Au compounds mainly originate from its strong relativistic effects.56,57,58,59 Considering the relativistic expansion of the 5d orbital and the contraction of the 6s orbital in Au,19,57 the appearance of other oxidation states, such as +4 and +6, is also possible. On the other hand, fluorine (F), having a rather large electronegativity and small atomic size, becomes a suitable candidate for realizing high oxidation states of Au (e.g. +3 in AuF3 and +5 in AuF5).60 Moreover, F-rich Au fluorides are of great interests due to their extremely high electron affinity, acting as strong oxidants and fluorination agents.61 Once, a +7 oxidation state of Au was claimed in AuF7 through the reaction of AuF5 with F2.62 However, a further study showed that it is the complex between AuF5 and F2.63 Additionally, +6 oxidation state of Au was predicted in AuF6 via quantum chemistry calculations63,64 but, unfortunately, it was shown to be metastable. However, AuF6- has been also observed in various salts21 and, in the same way that PtF6 can be obtained through oxidizing PtF6-,65 considering that Au just has one electron more than Pt, AuF6 might have a good chance to become stable under certain conditions. As it is well known, pressure can profoundly modify chemical properties of elements, overcome reaction barriers, and shorten interatomic distances, leading to the formation of some unusual stoichiometric compounds that are not accessible at ambient pressure.66,67,68,69,70 For example, it has been shown that the oxidative ability of F is further enhanced under pressure.71,72 Therefore, if Frich Au-F compounds become stable under high pressure, one might anticipate the appearance of new oxidation states in Au, which is not accessible at ambient pressure. Here, we conduct an extensive structure search to find the most stable structure for each AumFn (m = 1, n = 1 - 7 or m = 2, n = 1) composition at 0 K and the selected pressures of 1 atm and 25, 50, 100, 200 GPa with the aid of first-principles swarm structure search calculations.73,74 Besides reproducing the already known AuF3 and AuF5 structures, other unusual stoichiometries, such as AuF4 and AuF6, are found to be stable under high pressure. Interestingly, AuF4 and AuF6 have the structural character of a typical molecular crystal, allowing us to unambiguously assign the oxidation states of Au (+4 and +6, respectively). Moreover, the different high-pressure

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phase diagram between Au and Cu or Ag fluorides can be attributed to the strong relativistic effects of Au. 2. COMPUTATIONAL DETAILS Structural prediction was carried out as implemented in the CALYPSO program (crystal structure analysis by particle swarm optimization).73,74 CALYPSO is a leading structure prediction method in the field. The main advantage of this program is that it can efficiently determine the ground state or metastable structures just based on the known chemical composition. Its validity and efficiency have been confirmed through its application to a variety of known systems, ranging from elemental solids to binary and ternary compounds.73,75,76,77,78 More information about the method and structural predictions can be found in the Supporting Information. Structural relaxations and total energy calculations were performed within the framework of density functional theory (DFT)79,80 within the generalized gradient approximation as implemented by the Vienna Ab initio Simulation Package code.81 Here, the Perdew-BurkeErnzerhof (PBE)82 exchange-correlation functional was adopted in view of a compromise between accuracy and computational efficiency. The electron-ion interaction is described by pseudopotentials built within the scalar relativistic projector augmented wave method with 2s22p5 and 5d106s1 valence electrons for F and Au atoms, respectively. The cutoff energy was set at 700 eV, and appropriate Monkhorst-Pack k meshes were selected to ensure that all enthalpy calculations converged to less than 1 meV per atom. The dynamical stability of predicted structures was determined by phonon calculations using the finite displacement approach83 as implemented in the Phonopy code.84 3. RESULTS AND DISCUSSION To find the potential stable Au-F compounds, we have carried out extensive structural searches on Au-F compounds with various AumFn (m = 1, n = 1 - 7 or m = 2, n = 1) compositions at 0 K and the selected pressures of 1 atm and 25, 50, 100, 200 GPa. The predicted structure with the lowest enthalpy for each composition is then used to evaluate the enthalpy of formation with respect to elemental F and Au solids. The calculated convex hull for the Au-F system at different pressures are presented in Figures 1a and S1, which can be used to determine the relative stability of each composition. In general, the compounds sitting on the convex hull are thermodynamically stable with respect to elemental Au and F solids or other Au-F compounds. At ambient pressure, the already known stoichiometries AuF3 and AuF5 are readily identified in our structural search. In addition, the optimized crystal parameters of AuF3 (space group P6122, 6 formu-


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la units per cell) are a = b = 5.311 and c = 16.476 Å, in good agreement with the experimental values of a = b = 5.149 and c = 16.264 Å.85 These results indicate that our structure searching method and the adopted PBE functional are applicable to the Au-F system. At elevated pressures, it should be pointed out that several of unexpected compositions such as Au2F, AuF2, AuF4, and AuF6 become stable, whereas AuF5 decomposes into AuF4 and AuF6. In order to provide more information for experimental synthesis, we have also determined the stable pressure ranges of the considered compounds (Figures 1b and S1). In more detail, the reaction of AuF3 and Au, at pressures above 13.3 GPa, yields AuF2 (Figure S2a). AuF4 can be synthesized above 13.5 GPa by using AuF3 and AuF5 as precursors (Figure S2b). AuF6 can be obtained through compression of AuF5 and F2 at pressures above 5.0 GPa (Figure S2c). As will be discussed later, some of the stable Au-F compounds are molecular crystals. Therefore, in order to check the reliability of our calculations, we have also included van der Waals (vdW) interactions by employing optB86b-vdW and optB88-vdW functionals.86,87 Overall, considering vdW interactions just slightly lowers the synthesized pressures (Figure S2). Similar observations have been also found in (H2O)2He88 89 and XeHe2. In addition, for comparison, we have also analyzed the high-pressure phase diagrams of Ag-F and Cu-F systems (Figure S1). Despite Au, Ag, and Cu are in the same group, their high-pressure phase diagrams are very different. Specifically, the F-richest composition in Ag-F or Cu-F system is AgF4 or CuF4. Compared with AuF4, much higher pressures are needed to stabilize CuF4 or AgF4. This means that due to relativistic effects inner d electrons of Au are chemically more active than those of Cu and Ag. On the other hand, AuF and CuF are unstable in the whole considered pressure range, whereas AgF is stable. Moreover, some of the stable compounds undergo complex structural phase transitions under pressure, as shown in Figures 1 and S1. In the thermodynamic analysis of phase stability, contributions by entropy are neglected—they may have some impact in case high temperatures are needed for a synthesis and can, potentially, shift the required pressures for a synthesis to lower/higher values.90,91,92 Additionally, all the predicted compounds are dynamically stable in their stable pressure region without appearing any imaginary phonon modes (Figure S3).

Figure 1. (a) Phase stabilities of various Au-F compounds at 1 atm, 25 and 50 GPa. For clarity, we have offset the formation enthalpies of each composition by 0.2 and -0.4 eV at 25 and 50 GPa, respectively. The elemental Au solid with Fm-3m symmetry,93 and the C2/c94 and Cmca95 phases of elemental F2 solids were adopted in the enthalpy of formation calculations. (b) Pressurecomposition phase diagram of Au-F compounds. Among the predicted coinage metal fluorides, there are obvious differences in the crystal structures, such as symmetry, coordination number, and bond lengths. Here, we mainly take MF2 (M = Au, Ag, and Cu) as an example. AuF2 stabilizes into an orthorhombic structure above 13.3 GPa (space group Cmcm, 4 f.u. per cell, Figure 2a) and does not show any structural phase transition in the considered pressure range. In contrast, CuF2 and AgF2 are stable at ambient pressure96,97 and undergo complex phase transitions at high pressures (Figure S1). For AuF2, each Au atom coordinates with two F atoms with a quasi-linear formation. The shortest F-F distance of 2.20 Å in AuF2 at 50 GPa is significantly larger than the F-F covalent bond length (1.44 Å).71 CuF2 and AgF2, show a F vertex-sharing structure (Figure S4), and the coordination number of Ag or Cu with F is 4. More interestingly, the nearest Au atoms in AuF2 form zigzag chains along the c-axis with an interatomic distance of 2.57 Å. This distance is slightly longer than in the Au dimer (2.47 Å)98 and greatly shorter than the aurophilic interaction distance of 3.00 Å,57 indicating that zigzag Au chains play an important role stabilizing the structure. Similar Au chains have been observed in [AuSO4]2.99 When analyzing the M-F bond lengths, we can see that the CuF bond is the shortest one, while the longest one is not


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the Au-F bond but the Ag-F one (Table S2). This phenomenon is attributed to the relativistic bond-length contraction of Au,57 enhancing the bond strength in Au-F (Table S2).

Figure 2. Crystal structures of AuFn compounds. (a) Cmcm AuF2 at 50 GPa. (b) P6122 AuF3 at 1 atm. (c) P-1 AuF3 at 50 GPa. (d) I4/m AuF4 at 50 GPa. (e) Pnma AuF5 at 1 atm. (f) R-3 AuF6 at 50 GPa. Yellow and black spheres represent Au and F atoms, respectively. The already known phase of AuF3 with P6122 symmetry (Figure 2b) transforms into a P-1 structure (2 f.u. per cell, Figure 2c) under pressure. Both structures have quasi-square AuF4 units. Under compression, Cisfluorine single bridges convert into double fluorinebridges, similar to those in AuCl3.21 The stoichiometry of AuF4 stabilizes into a tetragonal structure above 13.5 GPa (2 f.u. per cell, Figure 2d) containing square-planar molecular units, as in HgF4.100 Notably, the nearest atomic distance of Au at 50 GPa is 3.85 Å, much longer than the aurophilic interaction distance of 3.0 Å,57 indicating the interaction between adjacent Au atoms is very weak, as will be discussed later. At ambient pressure AuF5 consists of dimeric Au pentafluoride units (Figure 2e) and becomes unstable above 17.3 GPa. AuF6 is predicted to be stable in a trigonal structure (space group R-3, 3 f.u. per cell, Figure 2f), consisting of octahedral AuF6 molecule units. Compared with AuF4, the nearest atomic distance of Au in AuF6 is even larger (4.22 Å). The shortest F-F distance is 2.22 Å, much longer than the covalent FF bond length of 1.44 Å, indicating that AuF6 is a typical molecular crystal. In view of the large electronegativity of F and the molecular crystal features in AuF4 and AuF6, the oxidation states of Au in AuF4 and AuF6 can be unambiguously assigned as +4 and +6, respectively. The

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analysis of the molecular orbitals of AuF4 shows that six electrons fill dz2, dxz, and dyz orbitals and one occupies the dxy orbital (Figure 3). Obviously, Au d7 electronic configuration in AuF4 is consistent with a +4 oxidation state. More interestingly, this is the first time a d7 electronic configuration is observed within a square-planar geometry.21,100,97 Unfortunately, we cannot explicitly assign the electronic occupation of Au in AuF6 due to the Jahn-Teller distorted octahedral structure.101

Figure 3. Molecular orbital plots of Au 5d orbitals in I4/m AuF4. To understand the nature of the chemical bonds and the formation mechanism of Au-F compounds, we calculated their projected density of states (PDOS), electron localization function (ELF),102 and crystal orbital Hamiltonian population (COHP).103,104 As shown in Figure 4, there is a pronounced overlap between Au 5d or 6s and F 2p orbitals near the Fermi level, showing that a charge transfer can occur from Au 5d or 6s to F 2p. This is further supported by the formation of a Au-F ionic bond, as shown in the ELF analysis (Figure S5). The appearance of the Au 5d component above the Fermi level indicates the depletion of 5d electrons in Au atoms. In addition, the Au 5d component above the Fermi level enhances with the increase of the F content, implying more Au 5d electrons transfer to F. COHP can be used to describe the contribution of the considered atomic pairs to the structural stability. In general, a negative COHP means a bonding state, while a positive COHP indicates an antibonding one. The more negative COHP it is below the Fermi level, the larger is the contribution. Below, AuF4 is taken as an example. Among the three COHPs considered, the Au-F bond COHP is the most negative one. Evidently, Au-F interaction is mainly responsible for its structural stability (Figure 4). Moreover, the integrated COHPs (ICOHP) up to the Fermi level scales with the bond strength. The resulting ICOHPs of Au-F, Au-Au, and F-F pairs are -1.958, -0.047, and 0.071 eV/pair, respectively, suggesting that the interaction of Au-Au and


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F-F bonds is rather weak. AuF6 also shows similar results (Table S3). Further analysis indicates that the interaction between Au and F mainly originates from the hybridization between Au 6s or 5d, and F 2p states (Figure S6). Interestingly, there is also a pressure-induced magnetic transition in AuF6 at 15 GPa (Figure S7), which also appears in FeH105 or Fe2SH3106 compounds.

Figure 4. PDOS of Cmcm AuF2, P-1 AuF3, I4/m AuF4, and R-3 AuF6 at 50 GPa and Pnma AuF5 at 1 atm. The vertical dashed lines indicate the Fermi energy. COHP for I4/m AuF4 at 50 GPa. 4. CONCLUSIONS In summary, we investigate the phase diagrams, crystal structures, and electron properties of coinage fluorides under high pressure by using first-principles calculations in combination with swarm structural searches. Interestingly, AuF4 and AuF6 stable molecular crystals with +4 and +6 oxidation states of Au have been identified. This finding not only fills the intermediate oxidation state of Au but also pushes Au to an unprecedented high oxidation state. Detailed analysis of its electronic properties shows that an uniformly distributed ionic Au-F bonding network plays a key role in determining its structural stability. Additionally, stabilization of AuF4 needs much lower pressures than CuF4 or AgF4. Our calculated highpressure phase diagrams of coinage fluorides provide a useful route for experimental synthesis, awaiting for a future confirmation. ASSOCIATED CONTENT Supporting Information Computational details, phase stabilities, crystal structures, and phonon spectra of M-F (M = Au, Ag, and Cu) compounds. ICOHP of AuF4 and AuF6 at 50 GPa.

AUTHOR INFORMATION Corresponding Author

*E-mail: [email protected] *E-mail: [email protected] ORCID Shoutao Zhang: 0000-0002-0971-8831 Guochun Yang: 0000-0003-3083-472X

Author Contributions

‡These authors contributed equally. Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS This work is supported by the Natural Science Foundation of China under Nos. 21573037, 11704062, 11534003, and 51732003; the Natural Science Foundation of Jilin Province (No. 20150101042JC); the Postdoctoral Science Foundation of China (under Grant No. 2013M541283); and the Fundamental Research Funds for the Central Universities (2412017QD006). YM acknowledges funding support from National Key Research and Development Program of China (No. 2016YFB0201200), Program for JLU Science and Technology Innovative Research Team, and Science Challenge Project No. TZ2016001. We greatly thank Prof. Aitor Bergara for his fruitful discussions and invaluable suggestions.

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Gold with +4 and +6 Oxidation States in AuF - American

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