Abstract
The reaction of the perfluorosulfanylvinyldiiron(I) complex [{Fe(CO)3}2{μ-C(SMe)(CF3)Cβ(CαF2)}] (1) with secondary mono- and diamines (L = Me2NH, (CH2)4NH, HN(CH2)4NH) in a 1:1 ratio in dichloromethane at room temperature led in a multistep reaction to the new monoaminocycloferrathiapentadiene compounds [{Fe(CO)3}2{μ-S(Me)C(CF3)CFCX}] (Χ = NMe2 (2), N(CH2)4 (3), N(CH2)4NH (4)) and [[{Fe(CO)3}2{μ-S(Me)C(CF3)CFC]2{μ-N(CH2)4N}] (5). However, when the reaction of 1 was conducted in THF with a large excess of amine, the diaminocycloferrathiabutene complexes [{Fe(CO)3}2{μ-S(Me)C(CF3)C(CX2)}] (X = NMe2 (6), N(CH2)4 (7)) and [{Fe(CO)3}2{μ-S(Me)C(CF3)C(CX)}] (X = MeN(CH2)2NMe (8), HN(CH2)2 NH (9)) were formed. It is suggested that these compounds form via initial nucleophilic attack at Cα to give the common zwitterionic intermediate [{Fe(CO)3}2{μ-S(Me)C(CF3)C(CFNX2)] (C). Thermally induced C−F bond activation is a feature of these reactions. Thermolysis of diaminocycloferrathiabutene compounds (6−9) in tetrahydrof...
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