WATER-SOLUBLE PHOSPHANES .3. WATER-SOLUBLE PRIMARY PHOSPHANES WITH AMMONIUM GROUPS NR(2)R' IN THE SIDE-CHAIN - DONOR-FUNCTIONALIZED AMPHIPHILES

Primary and secondary aminoalkylphosphanes R(2)N-(CH2)(m)-PH2 (R(2) = Me(2), nBu(2), C5H10, C4H8O, 2-(1-Methyl-2-pyrrolidinyl); m = 2, 3, 6, 10, 11; 1-6) or [R(2)N-(CH2)(m)]2PH (7, R(2) = C5H10; m = 2) are accessible by aminoalkylation of PH3 with ($) over bar omega-chloroalkylamines R(2)N-(CH2)(m)-Cl in the superbasic medium DMSO/KOH (DMSO = dimethylsulfoxide). By selective N-quaternization of 1, 2, 4-6 with R'I (R' = Me, CnH2n+1; n = 6-8, 12, 16, 18) in the two-phase system CH2Cl2/H2O novel primary phosphanes [R'R(2)N-(CH2)(m)-PH2]I-+(-) (11-16f) with quaternary ammonium groups in the alkyl side chain are obtained. The water solubility of 11-16f decreases with increasing chain length (n) of R'. 11 (R = R' = Me; m = 2) shows a trans conformation at the C2H4 bridge according to an X-ray structural analysis. Protonation of 1, 2, 4, 5 with HCl affords the water-soluble hydrochlorides [HR(2)N-(CH2)(m)-PH2]Cl-+(-) (19-22). The cationic primary phosphanes 11-16f are stable towards oxygen. By oxidation of 11 with one or two equivalents of H2O2 the primary phosphane oxide [Me(3)N-(CH2)(2)-P(O)H-2]I-+(-) (23) or the phosphonous acid [Me(3)N-(CH2)(2)-P(O)(OH)H]I-+(-) (23a) are formed. Hofmann degradation of 11 or 16c with KOH yields phosphirane in good yields. Reaction of 1, 2, 4-6 (L) with Fe-2(CO)(9) at ambient temperature yields stable complexes (CO)(4)FeL (26-30). Under more rigorous conditions Fe-3 clusters (31, 32) with free R(2)N groups are obtained.