The robust, readily available cobalt(iii) trication [Co(NH2CHPhCHPhNH2)3]3+ is a progenitor of broadly applicable chirality and prochirality sensing agents.

When NMR spectra of chiral racemic organic molecules containing a Lewis basic functional group are recorded in the presence of air and water stable salts of the cobalt(iii) trication [Co((S,S)-NH2CHPhCHPhNH2)3]3+ (23+), separate signals are usually observed for the enantiomers (28 diverse examples, >12 functional groups). Several chiral molecules can be simultaneously analyzed, and enantiotopic groups in prochiral molecules differentiated (16 examples). Particularly effective are the mixed bis(halide)/tetraarylborate salts Λ-23+ 2X-BArf- (X = Cl, I; BArf = B(3,5-C6H3(CF3)2)4), which are applied in CD2Cl2 or CDCl3 at 1-100 mol% (avg 34 and 14 mol%). Job plots establish 1 : 1 binding for Λ-23+ 2Cl-BArf- and 1-phenylethyl acetate (4) or 1-phenylethanol (10), and ca. 1 : 2 binding with DMSO (CD2Cl2). Selected binding constants are determined, which range from 7.60-2.73 M-1 for the enantiomers of 10 to 28.1-22.6 M-1 for the enantiomers of 4. The NH moieties of the C2 faces of the trication are believed to hydrogen bond to the Lewis basic functional groups, as seen in the crystal structure of a hexakis(DMSO) solvate of Λ-23+ 3I-. These salts rank with the most broadly applicable chirality sensing agents discovered to date.

Syntheses of Families of Enantiopure and Diastereopure Cobalt Catalysts Derived from Trications of the Formula [Co(NH2CHArCHArNH2)3]3.

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 Λ-[Co((S,S)-dpen)3]3+3Cl- [Λ-(S,S)-13+3Cl-] or Δ-(S,S)-13+3ClO4- (60-65%) with high degrees of selectivity. Anion metatheses (room temperature) and equilibrations (charcoal, CH3OH, 70 °C) show that the former is more stable than Δ-(S,S)-13+3Cl-, and the latter is more stable than Λ-(S,S)-13+3ClO4-. Additional anion metatheses lead to large families of lipophilic salts Λ- and Δ-(S,S)-13+2X-X'- [X/X' = Cl/BArf [BArf = B(3,5-C6H3(CF3)2)4], PF6/BArf, BF4/BArf, PhBF3/BArf, Cl/BArf20 [BArf20 = B(C6F5)4], BArf/BArf, BArf20/BArf20, BF4/BF4, PF6/PF6]. Mixed salts of the formula Λ- and Δ-[Co((S,S)-NH2CHArCHArNH2)3]3+2Cl-BArf- are similarly prepared (Ar = 4-C6H4n-Bu, 4-C6H4Cl, 4-C6H4CF3, 4-C6H4OCH3, α-naphthyl, ß-naphthyl, 2-C6H4OBn). The diastereotopic NHH' protons exhibit different 1H NMR signals; one shifts far downfield when X/X' = Cl/BArf (δ ca. 8.0 vs 4.0 ppm). This is believed to arise from hydrogen bonding between the two Cl- anions and the two C3 faces of the D3-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 Δ diastereomers.

Octahedral Werner complexes with substituted ethylenediamine ligands: a stereochemical primer for a historic series of compounds now emerging as a modern family of catalysts.

As reported by Alfred Werner in 1911-1912, salts of the formally D3 symmetric [Co(en)3]3+ (en = ethylenediamine) trication were among the first chiral inorganic compounds to be resolved into enantiomers, the absolute configurations of which are denoted Λ (left handed helix) or Δ (right handed helix). After a >100 year dormant period during which few useful reactions of these substitution inert complexes were described, carbon substituted derivatives have recently been found to be potent catalysts for enantioselective organic synthesis. This review systematically outlines the fascinating range of stereoisomers that can arise, such as conformers associated with the five membered chelate rings (λ/δ), alignment modes of the C-C bonds with the C3 symmetry axis (lel/ob), geometric isomers (fac/mer), and configurational diastereomers (R/S) arising from carbon stereocenters. These analyses demonstrate a profound stereochemical diversity that can be applied in catalyst optimization. Efforts are made to bridge the often orthogonal nomenclature systems inorganic and organic chemists employ to describe these phenomena.

Cobalt(III) Werner Complexes with 1,2-Diphenylethylenediamine Ligands: Readily Available, Inexpensive, and Modular Chiral Hydrogen Bond Donor Catalysts for Enantioselective Organic Synthesis.

In the quest for new catalysts that can deliver single enantiomer pharmaceuticals and agricultural chemicals, chemists have extensively mined the "chiral pool", with little in the way of inexpensive, readily available building blocks now remaining. It is found that Werner complexes based upon the D3 symmetric chiral trication [Co(en)3](3+) (en = 1,2-ethylenediamine), which features an earth abundant metal and cheap ligand type, and was among the first inorganic compounds resolved into enantiomers 103 years ago, catalyze a valuable carbon-carbon bond forming reaction, the Michael addition of malonate esters to nitroalkenes, in high enantioselectivities and without requiring inert atmosphere conditions. The title catalysts, [Co((S,S)-dpen)3](3+) ((S,S)-3 (3+)) 3X(-), employ a commercially available chiral ligand, (S,S)-1,2-diphenylethylenediamine. The rates and ee values are functions of the configuration of the cobalt center (Λ/Δ) and the counteranions, which must be lipophilic to solubilize the trication in nonaqueous media. The highest enantioselectivities are obtained with Λ and 2Cl(-)BArf (-), 2BF4 (-)BArf (-), or 3BF4 (-) salts (BArf (-) = B(3,5-C6H3(CF3)2)4 (-)). The substrates are not activated by metal coordination, but rather by second coordination sphere hydrogen bonding involving the ligating NH2 groups. Crystal structures and NMR data indicate enthalpically stronger interactions with the NH moieties related by the C3 symmetry axis, as opposed to those related by the C2 symmetry axes; rate trends and other observations suggest this to be the catalytically active site. Both Λ- and Δ-(S,S)-3 (3+) 2Cl(-)BArf (-) are effective catalysts for additions of ß-ketoesters to RO2CN=NCO2R species (99-86% yields, 81-76% ee), which provide carbon-nitrogen bonds and valuable precursors to α-amino acids.