Water-Soluble Phosphines. 6.(1) Tailor-Made Syntheses of Chiral Secondary and Tertiary Phosphines with Sulfonated Aromatic Substituents: Structural and Quantum Chemical Studies.

Chiral water-soluble secondary phosphines (2-6) were obtained by nucleophilic phosphination of FC(6)H(4)-4-SO(3)K (1a), FC(6)H(3)-2,4-(SO(3)K)(2) (1b), and FC(6)H(4)-2-SO(3)K (1c) with RPH(2) (R = Ph, 2,4,6-Me(3)C(6)H(2), 2,4,6-iPr(3)C(6)H(2)) in the superbasic medium DMSO/KOH by employing steric control of substitution at phosphorus by bulky substituents R and sulfonic groups in the ortho position of the aromatic ring systems in 1b or 1c. The secondary phosphines may be deprotonated in DMSO/KOH to give phosphido anions which on reaction with alkyl halides (PhCH(2)Cl, Br(CH(2))(3)Br, and C(12)H(25)Br) yield mono- or bidentate tertiary phosphines (7-10). Ligands of this type are alternatively accessible by nucleophilic arylation of secondary phosphines, e.g. Ph(Me)PH or Ph(H)P(CH(2))(3)P(H)Ph with 1a or 1b, respectively. The crystal structure of the starting material 1b.H(2)O (space group P2(1)/m) has been determined. In the solid state of 1b.H(2)O the individual molecules are interconnected by ionic interactions between the potassium cations and the SO(3)(-) anions. The C-F bond (C(1)-F 1.347(4) Å) is shorter than that in C(6)H(5)F (1.356(4) Å). The unit cell of 7a.0.5H(2)O (space group P&onemacr;), the first structurally characterized chiral phosphine with a sulfonated phenyl substituent, contains the two enantiomers. Due to the asymmetrical substitution at phosphorus the PC(3) skeletons are significantly distorted (P(1)-C(1,11,31) 1.864(10), 1.825(8), 1.841(7) Å). The electronic structure of sulfonated fluorobenzenes FC(6)H(5)(-)(n)()(SO(3)M)(n)() (M = K, NH(4), n = 1-3) is discussed on the basis of quantum chemical calculations. In particular, the reactivity difference toward nucleophilic phosphination within the series is rationalized in terms of steric factors and of the -I effect of the sulfonic groups.