Polymeric single-chain nanoparticles (SCNPs) prepared via the intramolecular cross-linking of single polymer chains pose promising prospects for various applications.1-4 We have recently developed an intramolecular collapse approach for the synthesis of organometallic nanoparticles using ROMP-derived polycyclooctadiene (pCOD) and the direct ligand exchange of Rh(I), Ir(I) and Ni(0) complexes.5-6 Herein, this methodology was employed for the preparation of high MW SCNPs from commercially available polybutadiene (PBD) which has the same repeat unit as pCOD. In addition, we describe the experimental and the theoretical study of the metal binding propensity of Rhodium towards PBDs with varying cis/trans content. These studies allowed further understanding of the formation mechanisms of these novel compounds and may help to design and synthesize novel SCNPs with new applications.
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