Synthesis of the gold analogue of the elusive doubly protonated water molecule

Schmidbaur, Hubert; Hofreiter, Stefan; Paul, Martin

doi:10.1038/377503a0

Cited by 124 publications

(77 citation statements)

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“…The halonium salts are not the first class where association between polyaurated onium salts is ligand and anion dependent: Pyramidal tetra(gold)arsonium cations and tri(gold)oxonium and -sulfonium cations {[(R 3 P)Au] n E} ϩ X Ϫ (E ϭ As͞n ϭ 4; E ϭ O,S͞n ϭ 3) were found as monomers and as dimers in lattices with different components (R 3 P and X), and the dimers may have different structures (29,(35)(36)(37). Likewise, methanium complexes {[(R 3 P)Au] 4 CH} ϩ BF 4 Ϫ appear to be associated in the crystal (38), whereas analogous C-substituted cations are monomeric (39).…”

Section: Discussionmentioning

confidence: 99%

Cluster self-assembly of di[gold(I)]halonium cations

Schmidbaur

Hamel

Mitzel

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

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Section: Discussionmentioning

confidence: 99%

Cluster self-assembly of di[gold(I)]halonium cations

Schmidbaur

Hamel

Mitzel

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

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“…Double-auration at halide anions to give V-shaped cations with small angles and short Au-Au distances are now known for chlorine and bromine (12). Oxide and alkoxide anions have been shown to accept up to four gold atoms to give V-shaped, trigonal pyramidal and even tetrahedral complexes (5b, 13,14). Sulfide (selenide, telluride) (5b, 14d) and thiolate (selenolate (5b), telluride (14c)) anions can reach coordination numbers from 2 to 6, and the resulting polynuclear cations have cluster structures clearly determined by Au-Au interactions.…”

Section: Gold Clustering In Polynuclear Compoundsmentioning

confidence: 99%

The aurophilicity phenomenon: A decade of experimental findings, theoretical concepts and emerging applications

2000

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The term 'aurophilicity' was introduced in 1989 to describe phenomena in the structural chemistry of gold which could not be readily rationalized by conventional concepts of chemical bonding. In the following decade the aurophilicity concept has been widely applied and supported by the results of many experimental as well as theoretical studies. It will be carried over into the new millennium as a continued incentive for investigations that will help in the understanding of the unique properties of gold.

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“…ab initio | boronium | hypercoordinate | cations | polycations H igher coordinate (1) main group compounds are of substantial theoretical (2-4) and experimental (5) (9) and oxygen f½ðo-CH 3 -C 6 H 4 Þ 3 PAu 4 Og 2þ (10) and determined their X-ray structures. The structures represent isolobal analogs of CH 6 2þ , NH 5 2þ , PH 5 2þ , SH 4 2þ and OH 4 2þ , respectively.…”

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confidence: 99%

Octahydriodo diborane (B ₂ H ₈ ) and its protonated cations containing five-, six-, and seven-coordinate boron atoms

Oláh

Prakash

Rasul

2012

Proc. Natl. Acad. Sci. U.S.A.

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Structures of octahydriodo diborane (B 2 H 8 ) 1 and its protonated 3, diprotonated 5, triprotonated 6, and tetraprotonated 7 ions were found to be calculationally viable minima at the MP2/cc-pVTZ level of theory. Each structure contains two-electron three-center (2e-3c) bonds. The protonation of 1 to form 3 was found to be strongly exothermic by 176.0 kcal∕mol. Subsequent protonation of 3 to form 5 was also found to be exothermic by 28.4 kcal∕mol. Further protonation of 5 to form 6 was, however, computed to be endothermic by 122.0 kcal∕mol whereas protonation of 6 to form 7 was again highly endothermic by 238.8 kcal∕mol. Deprotonation barriers of the ions were also computed.H igher coordinate (1) main group compounds are of substantial theoretical (2-4) and experimental (5) interest. Schmidbaur et al. have prepared a variety of monopositively charged higher coordinate gold complexes of main group elements (5). They have also prepared dipositively charged carbon f½ðC 6 H 5 Þ 3 PAu 6 Cg 2þ (6), nitrogen f½ðC 6 H 5 Þ 3 PAu 5 Ng 2þ (7), phosphorus f½ðC 6 H 5 Þ 3 PAu 5 Pg 2þ (8), sulfur (9) f½ðC 6 H 5 Þ 3 PAu 4 Sg 2þ (9) and oxygen f½ðo-CH 3 -C 6 H 4 Þ 3 PAu 4 Og 2þ (10) and determined their X-ray structures. The structures represent isolobal analogs of CH 6 2þ , NH 5 2þ , PH 5 2þ , SH 4 2þ and OH 4 2þ , respectively. They have also prepared a positively charged fivecoordinate boron complex of gold (11) f½ðC 6 H 5 Þ 3 PAu 4 B½PðC 6 H 11 Þ 3 g þ and determined its X-ray structure, but no dipositively charged gold complexes of boron have been reported to date.We have previously reported (12) the calculated structures of parent pentacoordiate BH 5 and derived the hexa-, hepta-, and octacoordinate boronium ions BH 6 þ , BH 7 2þ , and BH 8 3þ , respectively, with 1-4 two-electron three-center (2e-3c) bonds to be viable energy minima (Fig. 1). The structures were found to be isostructural, with isoelectronic carbon analogs CH 5 þ (13, 14), CH 6 2þ (15, 16), and CH 7 3þ (17) respectively.In continuation of our study of hypercoordinate compounds, we have extended our investigations to the next higher homologue of BH 5 , i.e., B 2 H 8 (which can be considered a complex of B 2 H 6 and H 2 or BH 5 and BH 3 ) and its protonated B 2 H 9 þ , B 2 H 10 2þ , B 2 H 11 3þ , and B 2 H 12 4þ ions at the ab initio MP2/ccpVTZ level. Computational MethodsGeometry optimizations, frequency calculations, and natural bond orbital (NBO) analyses were carried out with the Gaussian 09 program (18). The geometry optimizations were performed at the ab initio MP2/cc-pVTZ level. Vibrational frequencies at the MP2/cc-pVTZ//MP2/cc-pVTZ level were used to characterize stationary points as either minima (number of imaginary frequency (NIMAG ¼ 0) or transition states (NIMAG ¼ 1) and to evaluate zero point vibrational energies (ZPE), which were scaled by a factor of 0.95 (19). For improved energy, calculations were carried out using the accurate W1BD method (20, 21) as implemented in the Gaussian 09 program (18). Atomic charges at the MP2/cc-pVTZ//MP2/cc-p...

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Synthesis of the gold analogue of the elusive doubly protonated water molecule

Cited by 124 publications

References 14 publications

Cluster self-assembly of di[gold(I)]halonium cations

Cluster self-assembly of di[gold(I)]halonium cations

The aurophilicity phenomenon: A decade of experimental findings, theoretical concepts and emerging applications

Octahydriodo diborane (B ₂ H ₈ ) and its protonated cations containing five-, six-, and seven-coordinate boron atoms

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Synthesis of the gold analogue of the elusive doubly protonated water molecule

Cited by 124 publications

References 14 publications

Cluster self-assembly of di[gold(I)]halonium cations

Cluster self-assembly of di[gold(I)]halonium cations

The aurophilicity phenomenon: A decade of experimental findings, theoretical concepts and emerging applications

Octahydriodo diborane (B 2 H 8 ) and its protonated cations containing five-, six-, and seven-coordinate boron atoms

Contact Info

Product

Resources

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Octahydriodo diborane (B ₂ H ₈ ) and its protonated cations containing five-, six-, and seven-coordinate boron atoms