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(p-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 vs. 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 (ca. 1 h), although slower than the equivalent homogeneous reaction on the molecular species (<5 min). On the other hand, the subsequent rearrangement of [Rh(acac)(CO)(TPP@Pol)] and [RhCl(COD)(TPP@Pol)] within the TPP@Pol core and of [Rh(acac)(CO)(BMOPPP@Pol)] and [RhCl(COD)(BMOPPP@Pol)] within the BMOPPP@Pol core, leading respectively to [RhCl(CO)(TPP@Pol)(2)] and [RhCl(CO)(BMOPPP@Pol)(2)], is much more rapid (<30 min) than on the corresponding homogeneous process with the molecular species (>24 h).