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The solvent dependence suggests strong ion pairing in CDCl<jats:sub>3<\/jats:sub>, intermediate ion pairing in CD<jats:sub>2<\/jats:sub>Cl<jats:sub>2<\/jats:sub> and little ion pairing in [D<jats:sub>6<\/jats:sub>]acetone. <jats:sup>1<\/jats:sup>H, <jats:sup>19<\/jats:sup>F\u2005HOESY NMR spectra (HOESY: heteronuclear Overhauser effect spectroscopy) for <jats:bold>6<\/jats:bold> and <jats:bold>7<\/jats:bold> reveal a specific approach of the anion with respect to the brucinium cation plus subtle changes, which are related to the anion itself. Further, for carbocations <jats:bold>9<\/jats:bold>\u2013<jats:bold>12<\/jats:bold>, (all as BF<jats:sub>4<\/jats:sub><jats:sup>\u2212<\/jats:sup> salts) based on the NOE results, one finds marked changes in the relative positions of the BF<jats:sub>4<\/jats:sub><jats:sup>\u2212<\/jats:sup> anion. In these aryl cationic species the anion can be located either a)\u2005very close to the carbonium ion carbon b)\u2005in an intermediate position or c)\u2005proximate to the N or O atom of the <jats:italic>p<\/jats:italic>\u2010substituent and remote from the formally positive C atom. This represents the first example of such a positional dependence of an anion on the structure of the carbocation. DFT calculations support the experimental HOESY results. The solid\u2010state structures for <jats:bold>6\u2009c<\/jats:bold> and the novel Zeise's salt derivative, [brucinium][PtCl<jats:sub>3<\/jats:sub>(C<jats:sub>2<\/jats:sub>H<jats:sub>4<\/jats:sub>)], <jats:bold>6\u2009f<\/jats:bold>, are reported. Analysis of <jats:sup>195<\/jats:sup>Pt\u2005NMR and other NMR measurements suggest that the \u03b7<jats:sup>2<\/jats:sup>\u2010C<jats:sub>2<\/jats:sub>H<jats:sub>4<\/jats:sub> bonding to the platinum centre in <jats:bold>6\u2009f<\/jats:bold> is very similar to that found in K[PtCl<jats:sub>3<\/jats:sub>(C<jats:sub>2<\/jats:sub>H<jats:sub>4<\/jats:sub>)]. Field dependent <jats:italic>T<\/jats:italic><jats:sub>1<\/jats:sub> measurements on [brucinium][PtCl<jats:sub>3<\/jats:sub>(C<jats:sub>2<\/jats:sub>H<jats:sub>4<\/jats:sub>)] and K[PtCl<jats:sub>3<\/jats:sub>(C<jats:sub>2<\/jats:sub>H<jats:sub>4<\/jats:sub>)], are reported and suggested to be useful in recognizing aggregation effects.<\/jats:p>","DOI":"10.1002\/chem.200900021","type":"journal-article","created":{"date-parts":[[2009,6,5]],"date-time":"2009-06-05T15:02:01Z","timestamp":1244214121000},"page":"6848-6862","source":"Crossref","is-referenced-by-count":18,"title":["Ion Pairing and Salt Structure in Organic Salts through Diffusion, Overhauser, DFT and X\u2010ray 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