(750f) Nanoparticle SAMs As Molecular Rulers: Two Cu(I) Catalytic Centers Are Required for ‘Click' Catalysis

Walker, D. A., Northwestern University
Grzybowski, B., Northwestern University
Browne, K. P., Northwestern University

The ‘click’ reaction has become an exceedingly popular coupling reaction in organic chemistry, but the mechanism by which the reaction operates remains unknown.  It has been suggested that two Cu(I) catalytic centers are required for the mechanism, but to date there is no experimental evidence for this assumption. Here we employ on particle mixed self-assembled monolayers (mSAMs) to control the relative spacing between catalytic centers. This technique allows us to (i) experimentally prove that two catalytic centers are necessary for the ‘click’ reaction to occur and (ii) measure the critical separation at which a catalytically active pair of Cu(I) ions become inactive. This technique, beyond providing useful insights into the mechanism of the ‘click’ reaction, develops a platform for which other catalytic diads and triads can be investigated. A mixture of experimental and theoretical results will be resented.