The complex [FeH(η2-H2){PPh(OEt)2}4]BPh 4 reacts with terminal alkynes HC≡CR (R = p-tolyl, But or SiMe3) to give the corresponding alkenes H2C=CHR and the butenynyl derivative [Fe(η3-RC3CHR){PPh(OEt)2}4] +. In contrast, the related complex [FeH(η2-H2){P(OEt)3}4]BPh 4 reacts with terminal alkynes to yield alkenes and σ-acetylide [Fe(C≡CR){P(OEt)3}5]+ derivativs. Activated alkynes such as HC≡CCO2Me and MeO2CC≡CCO2Me react with both [FeH(η2-H2)L4]BPh4 [L = P(OEt)3 or PPh(OEt)2] to give vinyl derivatives [Fe{CH=CH(CO2Me)}L4]+ and [Fe{C(CO2Me)=CH(CO2Me)}L4]+, respectively. The characterization of the complexes by IR, 1H, 13C and 31P NMR spectroscopy is discussed.
Reactivity of iron(II) non-classical hydrides with alkynes
ALBERTIN, Gabriele;ANTONIUTTI, Stefano;BORDIGNON, Emilio
1992-01-01
Abstract
The complex [FeH(η2-H2){PPh(OEt)2}4]BPh 4 reacts with terminal alkynes HC≡CR (R = p-tolyl, But or SiMe3) to give the corresponding alkenes H2C=CHR and the butenynyl derivative [Fe(η3-RC3CHR){PPh(OEt)2}4] +. In contrast, the related complex [FeH(η2-H2){P(OEt)3}4]BPh 4 reacts with terminal alkynes to yield alkenes and σ-acetylide [Fe(C≡CR){P(OEt)3}5]+ derivativs. Activated alkynes such as HC≡CCO2Me and MeO2CC≡CCO2Me react with both [FeH(η2-H2)L4]BPh4 [L = P(OEt)3 or PPh(OEt)2] to give vinyl derivatives [Fe{CH=CH(CO2Me)}L4]+ and [Fe{C(CO2Me)=CH(CO2Me)}L4]+, respectively. The characterization of the complexes by IR, 1H, 13C and 31P NMR spectroscopy is discussed.
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