Homeomorphic Isomerization as a Design Element in Container Molecules; Binding, Displacement, and Selective Transport of MCl2 Species (M = Pt, Pd, Ni)

The dibridgehead diphosphine ((CH 2 ) 14 ) 3 P (1) can rapidly turn inside-out (homeomorphic isomerization) to give a mixture of in,in and out,out isomers. The exo directed lone pairs in the latter are able to scavenge Lewis acidic MCl 2 ; cagelike adducts of the in,in isomer, trans- Cl 2 (P((CH 2 ) 14 ) 3 P) (M = 2/Pt, 3/Pd, 4/Ni), then form. The NiCl 2 unit in 4 may be replaced by PtCl 2 or PdCl 2 , but 2 and 3 do not give similar substitutions. U-tubes are charged with CH 2 Cl 2 solutions of 1 (lower phase), an aqueous solution of K 2 MCl 4 (charging arm; M = Pt, Pd), and an aqueous solution of excess KCl (receiving arm). The MCl 2 units are then transported to the receiving arm until equilibrium is reached (up to 22 d). When the receiving arm is charged with KCN, transport is much faster (ca. 100 h) and higher K 2 MX 4 equilibrium ratios are obtained (≥96≤4). Analogous experiments with K 2 PtCl 4 /K 2 PdCl 4 mixtures show PdCl 2 transport to be more rapid. A similar diphosphine with longer methylene chains, P((CH 2 ) 18 ) 3 P, is equally effective. No transport occurs in the absence of 1, and other diphosphines or monophosphines assayed give only trace levels.