Diastereoselective Synthesis of P-Stereogenic Secondary Phosphine Oxides (SPOs) Bearing a Chiral Substituent by Ring Opening of (+)-Limonene Oxide with Primary Phosphido Nucleophiles.

Kinetic separation of the commercially available /-(+)-limonene oxide mixture by ring opening with primary phosphido nucleophiles LiPHR (R = ferrocenyl, Ph, Cy, -Bu, Mes* (Mes* = 2,4,6-(-Bu)CH)), followed by treatment with aqueous NHCl and HO, gave unreacted -(+)-limonene oxide and diastereoenriched mixtures of the secondary phosphine oxides (SPOs) PHR(-(+)-Lim-OH)(O), which could be separated by chromatography and/or recrystallization. This one-pot synthesis uses a cheap chiral material and commercially available primary phosphines to control the configuration of the new P-stereogenic SPOs, which are potentially useful as ligands for metal complexes in asymmetric catalysis.

Diastereoselective Coordination of P-Stereogenic Secondary Phosphines in Copper(I) Chiral Bis(phosphine) Complexes: Structure, Dynamics, and Generation of Phosphido Complexes.

Diastereoselective coordination of racemic secondary phosphines (PHRR') to Cu(I) precursors containing chiral bis(phosphines) (diphos*) was explored as a potential route to P-stereogenic phosphido complexes. Reaction of [Cu(NCMe)][PF] with chiral bis(phospholanes) gave [Cu(diphos*)][PF] (diphos* = ( R, R)-Me-DuPhos (1), ( R, R)-Et-DuPhos (2), or ( R, R)-Me-FerroLANE) (3)) or the mono(chelates) [Cu(diphos*)(NCMe) ][PF] (diphos* = ( R, R)- i-Pr-DuPhos, n = 2 (4); diphos* = ( R, R)-Me-FerroLANE, n = 1 (5)). Treatment of [Cu(NCMe)][PF] with diphos* and PHMe(Is) (Is = 2,4,6-( i-Pr)CH) gave mixtures of diastereomers of [Cu(( R, R)- i-Pr-DuPhos)(PHMe(Is))(NCMe)][PF] (6) and [Cu(( R, R)-Me-FerroLANE)(PHMe(Is))][PF] (7); two of the three expected isomers of the bis(secondary phosphine) complexes [Cu(( R, R)- i-Pr-DuPhos)(PhHP(CH) PHPh)][PF] ( n = 2 (8); n = 3 (9)) were formed preferentially in related reactions.

Synthesis, Structure, and Luminescence of Copper(I) Halide Complexes of Chiral Bis(phosphines).

For investigation of structure-property relationships in copper phosphine halide complexes, treatment of copper(I) halides with chiral bis(phosphines) gave dinuclear [Cu((R,R)-i-Pr-DuPhos)(μ-X)] [X = I (1), Br (2), Cl (3)], [Cu(μ-((R,R)-Me-FerroLANE)(μ-I)] (5), and [Cu((S,S)-Et-FerroTANE)(I)] (6), pentanuclear cluster CuI((S,S)-Et-FerroTANE) (7), and the monomeric Josiphos complexes Cu((R,S)-CyPF-t-Bu)(I) (8) and Cu((R,S)-PPF-t-Bu)(I) (9); 1-3, 5, and 7-9 were structurally characterized by X-ray crystallography. Treatment of iodide 1 with AgF gave [Cu((R,R)-i-Pr-DuPhos)(μ-F)] (4). DuPhos complexes 1-4 emitted yellow-green light upon UV irradiation at room temperature in the solid state.

Elucidation of the Fe(III) Gallate Structure in Historical Iron Gall Ink.

Synthetic, structural, spectroscopic and aging studies conclusively show that the main colorant of historical iron gall ink (IGI) is an amorphous form of Fe(III) gallate·xH2O (x = ∼1.5-3.2).