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.
The fluorine n.m.r. spectra of SF4, [(CH3)2CH]2NSF3, PF5:O(C2H5)2, SiF5−, SiF5:NH3−, and SiF5:HN(C2H5)2− have been recorded after treatment of glassware and reagents with [(CH3)3Si]2NH to remove H2O and HF impurities. A mechanism of intramolecular and intermolecular fluorine exchange, involving Lewis acid – Lewis base interaction and rapid equilibration of five and six coordinate geometries, is proposed.
. 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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