Preparation and Raman spectra of compounds of the trimercury(2+) cation. Crystal structure of trimercury bis(hexafluoroarsenate(V) Hg3(AsF6)2

Cutforth, Brent D.; Davies, C.; Dean, Philip A. W.; Gillespie, R. J.; Ireland, P. R.; Ummat, P. K.

doi:10.1021/ic50124a025

Cited by 52 publications

(24 citation statements)

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“…Liquid Sulfur Dioxide Triphenylphosphine When SO, solutions of triphenylphosphine and mercurous hexafluoroarsenate (8) In the region 1 < PPh,: Hg2,' < 2, n = 2 (see below), but higher coordination numbers may occur with a greater excess of ligand.…”

Section: Reactions Of Hg2(asf6) With Phosphines Inmentioning

confidence: 99%

“…The absence of metallic mercury in the solutions where PPh,: HgZ2' < 1 cannot be used to show the absence of disproportionation, since mercury is known to react with Hg2(AsF6), in SO, to give the yellow cation (8) and other polynuclear mercury cations (9,10). Thus one or both of the following reactions could have occurred in the yellow phosphine solutions : PPh,: Hg,,' > 0.5 and thus does not occur.…”

Section: Reactions Of Hg2(asf6) With Phosphines Inmentioning

confidence: 99%

“…If the Hg,PF,'+ salt is pumped for an extended period at room temperature all of the PF, is lost (as indicated by the infrared 1 0 1 spectrum) and the Raman spectrum shows only the 180 cm-' mercury-mercury stretching frequency of Hg,(AsF,), itself (8). The PF,-HgZ2+ system in SO, can clearly be described by 1420 -…”

Section: -mentioning

confidence: 99%

“…Tris(trifluor0-methy1)phosphine was the gift of C. J. Willis of this department. Mercurous hexafluoroarsenate and silver hexafluoroarsenate were synthesized as described previously (6,8). Tetramethylammonium hexafluoroarsenate, Me,NAsF,, was obtained by reaction of tetramethylammonium chloride with arsenic pentafluoride in anhydrous hydrogen fluoride.…”

Section: Reagentsmentioning

confidence: 99%

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Mercury(I) chemistry. Part II. Reactions of the mercurous ion with some ligands having the heavier Group VA or VIA elements as donor atoms

Dean¹,

Ibbott²

1976

Can. J. Chem.

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The reactions of Hg2(AsF6)2 with P(CF3)3, PF3, PCl3, P(CF3)Ph2, PClPh2, PPh3, P(OMe)3, AsPh3, SbPh3, SPPh3, SP(p-C6H4F)3, and SePPh3 in liquid sulfur dioxide have been studied. The last five ligands form insoluble 1:1 complexes, Hg2(AsF6)2•L, if L:Hg22+ ≤ 1, but disproportionation of the mercurous ion occurs if L:Hg22+ > 1; the 1:1 mercurous complexes have been characterized by analysis and vibrational spectroscopy. There is no evidence for complexation of P(CF3)3. PPh3 and P(OMe)3 cause disproportionation of the mercurous ion under all conditions; Hg(PPh3)22+ and Hg(P(OMe)3)22+ have been characterized by 13C and 1H nmr respectively. When P(CF3)Ph2:Hg22+ ≤ 1 soluble Hg2(P(CF3)Ph2)2+ is formed; the 19F and 13C nmr spectra of this complex are reported, as are those of Hg(P(CF3)Ph2)22+. In the system PF3–Hg2(AsF6)2–SO2 no disproportionation occurs; 19F nmr provides evidence that Hg2PF32+ and, probably, Hg2(PF3)22+ are formed. 1J(P–F) in mercurous and silver(I) complexes of PF3 is of unusually large magnitude. The 13C nmr spectra of Hg(PPh3)22+, Hg2(P(CF3)PPh2)2+, and Hg(P(CF3)Ph2)22+, are consistent with the occurrence of little metal-to-phosphorus back-bonding in these phosphine complexes. The relationship between the net electron donating ability of a phosphine and the nature of its interaction with the mercurous ion is discussed.

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Section: Reactions Of Hg2(asf6) With Phosphines Inmentioning

confidence: 99%

Section: Reactions Of Hg2(asf6) With Phosphines Inmentioning

confidence: 99%

Section: -mentioning

confidence: 99%

Section: Reagentsmentioning

confidence: 99%

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Mercury(I) chemistry. Part II. Reactions of the mercurous ion with some ligands having the heavier Group VA or VIA elements as donor atoms

Dean¹,

Ibbott²

1976

Can. J. Chem.

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“…The complexes were synthesized by mixing solutions of the hydrocarbon and mercurous hexafluoroarsenate (10) in liquid sulfur dioxide:…”

Section: Results and Discussion Preparation Of The Complexesmentioning

confidence: 99%

Mercury(I) chemistry. Part I. Complexes of the mercurous ion with some arenes

Dean¹,

Ibbott²,

Stothers³

1976

Can. J. Chem.

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. Can. J. Chem. 54, 166 (1976). A wide range of arene complexes of the mercurous ion has been prepared from mercurous hexafluoroarsenate and the appropriate arene in liquid sulfur dioxide. Raman spectroscopy confirmed the integrity of the dimeric HgZ2+ cation in these complexes. 13C nuclear magnetic resonance spectroscopy showed that Hg,,+-arene complexes exist in sulfur dioxide solution. The 13C data allowed the estimation of formation constants for the hexamethylbenzene, p-xylene, and p-dichlorobenzene complexes together with the 13C chemical shifts for the bound substrates in these cases. The 13C chemical shift changes (relative to the free substrate) on addition of HgZ2+ to SO, solutions of various methylated benzenes are compared with those occurring on complexation of the same arenes by the argentous ion and the Cr(CO), moiety. In mercurous ion-arene complexes, it is concluded that the cation is involved in a localized interaction with the arene and that there are preferred binding sites. These sites may be identified by the complexation shifts for the Ag+-and HgZ2+-arene complexes. On a prepare une grande variete de complexes d'artnes avec des ions mercureux en faisant rtagir de l'hexafluoroarsenate mercureux et des artnes appropries dans l'anhydride sulfureux liquide. La spectroscopie Raman a confirme l'integritt du cation dimtre HgZ2+ dans ces complexes. La rmn du I3C montre que des complexes Hg,"-arene existent en solution dans I'anhydride sulfureux. Les donnees 13C permettent d'estimer les constantes de formation des complexes avec I'hexamkthylbenztne, ie p-xylene et lep-dichlorobenztne de m&me que les deplacements chimiques 13C pour les substrats lies dans ces cas. Les changements dans les dkplacements chimiques 13C (par rapport au substrat libre) par addition de HgZ2+ aux solutions dans le SO, pour les divers benzenes methyles sont compares avec ceux qui se produisent lors de la complexation des m&mes artnes avec des ions argenteux et des moitits Cr(CO),. Dans les complexes ion mercureux -arene, on en conclut que le cation est implique dans une interaction localisee avec l'arene et qu'il y a des sites de liaisons preferees. On a identifie ces sites par les dtplacements de complexation pour des complexes Ag+-et Hgz2+-arene.[Traduit par le journal]

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Hard Acid and Soft Base Stabilisation of Di- and Trimercury Cations in Benzene Solution – A Spectroscopic, X-ray Scattering, and Quantum Chemical Study

Ulvenlund¹,

Rosdahl

Fischer

et al. 1999

Eur. J. Inorg. Chem.

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Hg2Cl2 dissolves in GaCl3/benzene solution to yield Hg22+ and chlorogallate(III) ions, GanCl3n+1−. In such solutions, Hg22+ can be reduced to Hg32+ by metallic mercury. Solubility measurements show that one mol of Hg is oxidised per mol of Hg22+. The Hg32+ ion gives a strong band at 110 cm−1 in the Raman spectrum and Hg–Hg correlations at about 2.60 and 5.15 Å in the radial distribution function obtained by liquid X‐ray scattering. – Hg32+ can also be synthesised in high yield by direct oxidation of metallic mercury by GaIII in GaCl3/benzene solution. In contrast, mercury is insoluble in neat liquid GaCl3 and only sparingly soluble in GaCl3/KCl melts. It therefore seems likely that the thermodynamic stabilisation of subvalent mercury species in benzene solution not only relies on the traditional acid stabilisation provided by the hard Lewis acid GaCl3, but also on a “soft‐base stabilisation” provided by interactions between the aromatic molecules and the cations. Evidence for such specific interactions between Hgm2+ cations and C6H6 are observed in the Raman spectra: The totally symmetric C6H6 band at 991 cm−1 is found to split in the presence of Hgm2+ ions and to give new peaks at 978 (m = 2) and 982 (m = 3) cm−1. – In order to further elucidate the cluster–arene interactions, ab initio and density functional calculations were performed for the model compounds Hgm(C6H6)22+ and HgmCl2(C6H6)2, m = 2 and 3. The calculations show that both models represent coordinations modes which are feasible for Hgm2+ ions. However, the calculated vibrational frequencies for the Hgm(C6H6)22+ models with η1/quasi‐η3 coordination of the benzene molecules along the Hg–Hg vector are most consistent with the body of experimental and literature data. The counterions are thus suggested to occupy secondary coordination sites.

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Preparation and Raman spectra of compounds of the trimercury(2+) cation. Crystal structure of trimercury bis(hexafluoroarsenate(V) Hg3(AsF6)2

Cited by 52 publications

References 2 publications

Mercury(I) chemistry. Part II. Reactions of the mercurous ion with some ligands having the heavier Group VA or VIA elements as donor atoms

Mercury(I) chemistry. Part II. Reactions of the mercurous ion with some ligands having the heavier Group VA or VIA elements as donor atoms

Mercury(I) chemistry. Part I. Complexes of the mercurous ion with some arenes

Hard Acid and Soft Base Stabilisation of Di- and Trimercury Cations in Benzene Solution – A Spectroscopic, X-ray Scattering, and Quantum Chemical Study

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