Affiliation:
1. Homogeneous Supramolecular and Bio-Inspired Catalysis Van't Hoff Institute for Molecular Science (HIMS) University of Amsterdam Science Park 904 1098 XH Amsterdam The Netherlands
2. Nobian Zutphenseweg 10 7418 AJ Deventer The Netherlands
3. Current address: KLK Kolb Specialties Langestraat 167 7491 AE Delden The Netherlands
Abstract
AbstractAtom transfer radical addition (ATRA) of halogenated compounds with alkenes is well established but primary alkyl chlorides are understudied because of the difficult C−Cl bond activation. In this paper, we show that TONs of 61 can be achieved in the ATRA of ethyl chloroacetate onto styrene with [Cp*Ru(Cl)2(PPh3)] and 1,1′‐azobis(cyclohexanecarbonitrile) (ACHN) as a radical initiator, representing a three‐fold improvement compared to previous reports. New catalyst precursors of the type [Cp*Ru(Cl)2(PR3)] were synthesized and tested (R=Me, Et, Cy, Ph, p‐CF3C6H4 and p‐MeOC6H4). The kinetic reaction profiles were studied using in situ ATR−FTIR spectroscopy. Among these complexes, [Cp*Ru(Cl)2(PPh3)] gave the best yields while [Cp*Ru(Cl)2(PMe3)] showed the highest rate. While rates correlate with redox potentials (electronics), our investigation reveals that substrate sterics are important for the overall yield. Density functional theory calculations suggest an open‐shell singlet pathway, where polymerization is kinetically disfavored, explaining the selectivity towards ATRA products.