摘要 : Monocationic amphiphilic tertiary phosphines [RMe(2)N-(CH2)(n)-PR'(2)](+) X(-) (1-3) obtained by P-alkylation of the corresponding primary phosphines (R' = H) form stable tungstencarbonyl-, Rh(I)-olefin- and square planar Pd(II)-c... 展开 Monocationic amphiphilic tertiary phosphines [RMe(2)N-(CH2)(n)-PR'(2)](+) X(-) (1-3) obtained by P-alkylation of the corresponding primary phosphines (R' = H) form stable tungstencarbonyl-, Rh(I)-olefin- and square planar Pd(II)-complexes (4-8a). Stepwise protonation of [Me(2)N-(CH2)(2)]P-3 (9) by Ph(3)P . HBr or aqueous HCl affords tricationic tertiary phosphine ligands, e.g. {[HMe(2)N-(CH2)(2)]P-3}(3+) 3X(-) (13, 13b) and the phosphonium salt {[HMe(2)N-(CH2)(2)]P-3-H}(4+) 4Cl(-) (13a). The pK(a)-values 9.67, 8.86, 7.92 and 1.9 have been obtained by titration of 13a with NaOH in aqueous solution. Highly charged Pd(II)-complexes (16a, 16b) with extreme water solubilities were obtained from 13 and PdBr2 or by N-protonation of cis-PdCl2(9)(2) with HCl. The crystal structures of 13 . 0.5H(2)O and {trans-{[HMe(2)N-(CH2)(2)]P-3}2PdCl2}(6+) 6Cl(-). 2MeOH (16b) (space group C2/c) have been determined. While the P(... N)(3) skeleton of the trication in 13 is almost flat, it is folded back on coordination to palladium(II) in 16b. [References: 50] 收起