Self-Separating Homogeneous Copper (I) Catalysts David E. Bergbreiter*, Patrick N. Hamilton, and Nirmal M. Koshti Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842-3012, USA bergbreiter@tamu.edu Supplementary Material Table of Contents Chemicals S1 Synthesis of N,N-Bis(2-Pyridylmethyl)-N-Propargylamine S2 Synthesis of 1,3-N,N,N′,N′-Tetraethyl-2-N′′-Propargyldiethylenetriamine S2 Synthesis of PIB-Cu(I) complex 4 S2 Synthesis of PIB-Cu(I) complex 3 S2 ATRP polymerization of styrene with 3 S3 Recycling of 3 in the ATRP polymerization of styrene S3 ATRP polymerization of methyl methacrylate with 3 S3 Synthesis of PIB-Ligand 5 S4 General procedure for the ATRP polymerization of styrene with 3 and 5 S4 Recycling of 3 and 5 in the ATRP polymerization of styrene S4 General procedure for ‘click’ reactions S4 References for Supplementary Materials S5 Chemicals. Styrene (sty, 99%, Aldrich) was distilled, stored under nitrogen in a freezer, and passed through a column filled with basic alumina prior to use. CuCl (97%, Alfa Aesar) and tin (II) 2-ethylhexanoate (95%, Aldrich) were used as received. Propargyl amine (98%, Aldrich), 2-picolyl chloride hydrochloride (98%, Aldrich), ethyl 2-bromoisobutyrate (98%, Aldrich), 2-pyridinecarboxaldehyde and other solvents were used without further purification. Polyisobutylene (PIB) was obtained from BASF (Glissopal 1000 or 2300). 1 H NMR spectra were obtained on Varian Inova 300 or Mercury 300 spectrometers at 300 MHz and reported in ppm referenced to CDCl 3 . 13 C NMR spectra were obtained on Varian Inova 300 or Mercury 300 spectrometers at 75 MHz and reported in ppm referenced to the chloroform contaminant in CDCl 3 unless otherwise stated. Gel permeation chromatography was performed using a Viscotek triple detector system using a GMHx1 column set with tetrahydrofuran as the eluting solvent. A flow rate of 1 mL/min was used and molecular weights and polydispersity were determined using polystyrene standards using the software supplied by Viscotek. S1