Properties of WAu<sub>12</sub>

Autschbach, Jochen; Heß, Bernd A.; Johansson, Mikael P.; Neugebauer, Johannes; Patzschke, Michael; Pyykkö, Pekka; Reiher, Markus; Sundholm, Dage

doi:10.1039/b310395a

Cited by 109 publications

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References 63 publications

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“…[28] Experimentell wurde es bereits im selben Jahr durch Wang et al in der Gasphase nachgewiesen. [29] Autschbach et al [30] schlugen eine geschlossenschalige 18-Elektronen-Bindungssituation für das zentrale W-Atom mit einer deutlichen Population der p-Valenzorbitale vor. Diese Tatsache ist jedoch für das Mo-Atom in 1 H anders.…”

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Zwölf Einelektronenliganden koordinieren an ein Metallzentrum: Struktur und Bindung von [Mo(ZnCH₃)₉(ZnCp*)₃]

et al. 2008

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Zwölf Einelektronenliganden koordinieren an ein Metallzentrum: Struktur und Bindung von [Mo(ZnCH₃)₉(ZnCp*)₃]

et al. 2008

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“…This replacement is known to have significant effects on structures of gold clusters. [2] Since no auxiliary basis sets of TZVPP or TZVPP(2f) quality are available for Au in Turbomole 5.4, we have used the TZVP auxiliary basis instead. Test calculations showed that this has a negligible effect on the results.…”

Section: Computational Detailsmentioning

confidence: 99%

“…Cage-like clusters can exhibit a pronounced effect on the NMR chemical shift of interstitial atoms; one example is the extraordinarily large 183 W chemical shielding that has been recently predicted for the WAu 12 cluster. [2] On the other hand, in interstitial carbides 13 C nuclei are known to be very strongly deshielded. Other examples are the 13 C NMR chemical shifts of a series of interstitial carbides in transition-metal clusters.…”

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confidence: 99%

The “Invisible” ¹³C NMR Chemical Shift of the Central Carbon Atom in [(Ph₃PAu)₆C]²⁺: A Theoretical Investigation

Guennic¹,

Neugebauer²,

Reiher³

et al. 2005

Chemistry A European J

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The experimental 13C NMR chemical shift of the central carbon atom in the octahedral [(Ph3PAu)6C]2+ cluster was investigated on the basis of relativistic density functional calculations. In order to arrive at independent model conclusions regarding the value of the chemical shift, a systematic study of the dependence of the cluster structure on the phosphine ligands, the chosen density functionals, and the basis set size was conducted. The best structures obtained were then used in the NMR calculations. Because of the cage-like cluster structure a pronounced deshielding of the central carbon nucleus could have been expected. However, upon comparison with the 13C NMR properties of the related complex [C{Au[P(C6H5)2(p-C6H4NMe2)]}6]2+, Schmidbaur et al. have assigned a signal at delta=135.2 ppm to the interstitial carbon atom. Our calculations confirm this value in the region of the aromatic carbon atoms of the triphenylphosphine ligands. The close-lying signals of the 108 phenyl carbon atoms can explain the difficulties of assigning them experimentally.

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“…Our starting point was the Au/H chemical analogy [3][4][5][6] and the recent discovery of the icosahedral, 18-valence-electron species WAu 12 . [7][8][9] Its hydrogen analogues turned out to exist as stable minima but to have either a mixture of M-H and M(η 2 -H 2 ) bonds or only dihydrogen bonds. The literature on such bonds has been reviewed by Kubas 10 and Maseras et al 11 The previous M-H n species had n values up to 9, occurring in ReH 9 2-.…”

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confidence: 99%

“…[7][8][9] Its hydrogen analogues turned out to exist as stable minima but to have either a mixture of M-H and M(η 2 -H 2 ) bonds or only dihydrogen bonds. The literature on such bonds has been reviewed by Kubas 10 and Maseras et al 11 The previous M-H n species had n values up to 9, occurring in ReH 9 2-. Thus, the new systems with n ) 12 would be a new record for metal hydrides.…”

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How Many Hydrogen Atoms Can Be Bound to a Metal? Predicted MH₁₂ Species

Gagliardi

Pyykkoe

2005

ChemInform

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Metal hydrides are of considerable current interest, among other reasons, as potential hydrogen storage systems. 1,2 A design target of 6.5 wt % H has been regarded as adequate. We here report molecular-level calculations for a series of potential species of type MH 12 , where M is a group 6 atom, Cr, Mo, and W. They turned out to be stable as single molecules. In a hypothetical solid Li- (VH 12 ), the percentage would be 17, leaving plenty of room for adjustments. The isoelectronic ions VH 12 -, TiH 12 2-, and MnH 12 + also turned out to be stable. Our starting point was the Au/H chemical analogy [3][4][5][6] and the recent discovery of the icosahedral, 18-valence-electron species WAu 12 . 7-9 Its hydrogen analogues turned out to exist as stable minima but to have either a mixture of M-H and M(η 2 -H 2 ) bonds or only dihydrogen bonds. The literature on such bonds has been reviewed by Kubas 10 and Maseras et al. 11 The previous M-H n species had n values up to 9, occurring in ReH 9 2-. Thus, the new systems with n ) 12 would be a new record for metal hydrides. A single hydride ion in solid hydrogen is reported to form (H -)(H 2 ) 12 with n ) 24. 12 All species were studied using density functional theory, DFT, with the B3LYP exchange-correlation functional and second-order perturbation theory, MP2. For H, the 6-31g* basis set was used. For all metal atoms, energy-adjusted Stuttgart ECPs were used in order to take into account relativistic effects. 13 The number of valence electrons is 12 for Ti, 13 for V, 14 for Cr, Mo and W, and 15 for Mn. The 6s5p3d valence basis sets accompanying the ECPs were used 14 for all atoms. The calculations were repeated also with larger basis sets, in which the metal valence basis set were increased with one f function 6s5p3d1f. The H basis used in this second set of calculations was of the 6-31g** type, contracted to 2s1p. We shall report only the results obtained with the larger basis set. Equilibrium geometries and harmonic frequencies were computed for all species at the DFT level of theory and MP2 level of theory. To investigate the electronic structure of these species, some singlepoint energy calculations at the DFT-optimized geometries were repeated using the complete active space (CAS) SCF method 15 with dynamic correlation added by second-order perturbation theory (CASPT2). 16 The CASSCF/CASPT2 calculations were performed with all electron basis sets of the ANO type for all atoms. The exponents were optimized using the Douglas-Kroll Hamiltonian. The contracted basis set was 6s5p3d2f for Cr, 7s6p4d2f for Mo, 7s6p4d2f for W, and 2s1p for H. The active space included 12 active electrons in 12 active orbitals, which are the bonding and antibonding linear combination of the metal d orbitals and hydrogen s orbitals. Note that the four orbitals, mainly bonding to M np and ns AOs lie further down. The programs Gaussian03 and MOL-CAS6.0 17 were employed.We shall discuss first the neutral molecules and then the ionic species. All the MH 12 species were found to be local minima, wi...

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Properties of WAu₁₂

Cited by 109 publications

References 63 publications

Zwölf Einelektronenliganden koordinieren an ein Metallzentrum: Struktur und Bindung von [Mo(ZnCH₃)₉(ZnCp*)₃]

Zwölf Einelektronenliganden koordinieren an ein Metallzentrum: Struktur und Bindung von [Mo(ZnCH₃)₉(ZnCp*)₃]

The “Invisible” ¹³C NMR Chemical Shift of the Central Carbon Atom in [(Ph₃PAu)₆C]²⁺: A Theoretical Investigation

How Many Hydrogen Atoms Can Be Bound to a Metal? Predicted MH₁₂ Species

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Properties of WAu12

Cited by 109 publications

References 63 publications

Zwölf Einelektronenliganden koordinieren an ein Metallzentrum: Struktur und Bindung von [Mo(ZnCH3)9(ZnCp*)3]

Zwölf Einelektronenliganden koordinieren an ein Metallzentrum: Struktur und Bindung von [Mo(ZnCH3)9(ZnCp*)3]

The “Invisible” 13C NMR Chemical Shift of the Central Carbon Atom in [(Ph3PAu)6C]2+: A Theoretical Investigation

How Many Hydrogen Atoms Can Be Bound to a Metal? Predicted MH12 Species

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Properties of WAu₁₂

Zwölf Einelektronenliganden koordinieren an ein Metallzentrum: Struktur und Bindung von [Mo(ZnCH₃)₉(ZnCp*)₃]

Zwölf Einelektronenliganden koordinieren an ein Metallzentrum: Struktur und Bindung von [Mo(ZnCH₃)₉(ZnCp*)₃]

The “Invisible” ¹³C NMR Chemical Shift of the Central Carbon Atom in [(Ph₃PAu)₆C]²⁺: A Theoretical Investigation

How Many Hydrogen Atoms Can Be Bound to a Metal? Predicted MH₁₂ Species