Coordination Chemistry inside Polymeric Nanoreactors: Metal Migration and Cross-Exchange in Amphiphilic Core-Shell Polymer Latexes

A well-defined amphiphilic core-shell polymer functionalized with bis( -methoxy-phenylphosphino)phenylphosphine (BMOPPP) in the nanogel (NG) core has been obtained by a convergent RAFT polymerization in emulsion. This BMOPPP@NG and the previously-reported TPP@NG (TPP = triphenylphosphine) and core cross-linked micelles (L@CCM; L = TPP, BMOPPP) having a slightly different architecture were loaded with [Rh(acac)(CO)₂] or [RhCl(COD)]₂ to yield [Rh(acac)(CO)(L@Pol)] or [RhCl(COD)(L@Pol)] (Pol = CCM, NG). The interparticle metal migration from [Rh(acac)(CO)(TPP@NG)] to TPP@NG is fast at natural pH and much slower at high pH, the rate not depending significantly on the polymer architecture (CCM NG). The cross-exchange using [Rh(acac)(CO)(BMOPPP@Pol)] and [RhCl(COD)(TPP@Pol)] (Pol = CCM or NG) as reagents at natural pH is also rapid ( 1 h), although slower than the equivalent homogeneous reaction on the molecular species (