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Correlation of Metal Spin State with Catalytic Reactivity: Polymerizations Mediated by α-Diimine–Iron Complexes


  • The Engineering and Physical Sciences Research Council of the United Kingdom and the Natural Sciences and Engineering Research Council of Canada are thanked for funding.


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The mechanism of styrene polymerization by α-diimine iron complexes correlates with the metal spin state of the catalyst. Experimental and theoretical studies indicate that high-spin catalysts are halogenophilic, resulting in atom transfer radical polymerization (ATRP), while intermediate-spin complexes are carbophilic giving rise to catalytic chain transfer (CCT, see graph).