Title: Secondary α-hydrogen kinetic isotope effects in nucleophilic additions to ferrocenyl-stabilised carbocations
Abstract:The secondary α-hydrogen kinetic isotope effects upon the solvolyses of Fc2C+H (1a) and p-MeCO6-H4C+HFc (1b)(Fc = ferrocenyl) in H2O, H2O–MeCN, and H2O–MeOH (kfH/kfD=ca. 0·9), and upon the acid hetero...The secondary α-hydrogen kinetic isotope effects upon the solvolyses of Fc2C+H (1a) and p-MeCO6-H4C+HFc (1b)(Fc = ferrocenyl) in H2O, H2O–MeCN, and H2O–MeOH (kfH/kfD=ca. 0·9), and upon the acid heterolyses of the corresponding alcohols (krH/krD=ca. 1·1), suggest that there is appreciable C ⋯ O bond formation in the transition state for carbocation solvolysis; for additions of HO–, N3–, and BH4– to (1a), kfH/ktD=ca. 1·0, indicating 'early' carbocation-like transtition states for these reactions, whereas intermediate values (kfH/kfD=ca. 0·96) are found for additions of primary amines.Read More
Publication Year: 1979
Publication Date: 1979-01-01
Language: en
Type: article
Indexed In: ['crossref']
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Cited By Count: 1
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