Aerobic reactions of CoX2 (X = OAc, Cl) or Co(ClO4)(2) with (S,S)-1,2-diphenylethylenediamine [(S,S)-dpen] in CH3OH, followed by HCl or HClO4 additions, give the diastereomeric lipophobic salts ?-[Co((S,S)-dpen)(3)](3+)3Cl [Delta-(S,S)-1(3+)3Cl ] or Delta-(S,S)-1(3+)3ClO(4) (6065%) with high degrees of selectivity. Anion metatheses (room temperature) and equilibrations (charcoal, CH3OH, 70 C) show that the former is more stable than Delta-(S,S)-1(3+)3Cl , and the latter is more stable than Delta-(S,S)-1(3)+3ClO(4). Additional anion metatheses lead to large families of lipophilic salts Delta- and Delta-(S,S)-13+2XX' [X/X' = Cl/BArf [BArf = B(3,5-C6H3(CF3)(2))(4)], PF6/BArf, BF4/BArf, PhBF3/BArf, Cl/BArf(20) [BArf(20) = B(C6F5)(4)], BArf/BArf, BArf(20)/BArf(20), BF4/BF4, PF6/PF6]. Mixed salts of the formula Delta- and Delta-[Co((S,S)-NH2CHArCHArNH2)(3)](3+)2Cl BArf are similarly prepared (Ar = 4-C(6)H(4)n-Bu, 4-C6H4Cl, 4-C6H4CF3, 4-C6H4OCH3, alpha-naphthyl, beta-naphthyl, 2-C6H4OBn). The diastereotopic NHH' protons exhibit different 1H NMR signals; one shifts far downfield when X/X' = Cl/BArf (delta ca. 8.0 vs 4.0 ppm). This is believed to arise from hydrogen bonding between the two Cl anions and the two C-3 faces of the D-3-symmetric trication, each of which feature three synperiplanar NH groups. When all of the anions are poor hydrogen-bond acceptors (e.g., BArf , BF4 , ClO4 ), equilibria favor Delta diastereomers.