Oxidative–elimination reactions of zerovalent iron and ruthenium complexes

Abstract

Ultraviolet irradiation of a solution of trans-(Et₃P)₂Fe(CO)₃ in liquid sulphur dioxide gives trans-(Et₃P)₂Fe(CO)₂(SO₂), which reacts with hydrogen iodide to form cis-(CO)₂-trans-(Et₃P)₂Fel₂. Treatment of trans-(PhPMe₂)₂Fe(CO)₃ with iodine or hydrogen iodide affords cis-(CO)₂-trans-(PhPMe₂)₂Fel₂. trans-(Ph₂PMe)₂Ru(CO)₃ and iodine react to give cis-(CO)₂-trans-(Ph₂PMe)₂Rul₂, whereas, a mixture of isomers of (CO)₂[EtC(CH₂O)₃P]₂Rul₂ is obtained from trans-[EtC(CH₂O)₃P]₂Ru(CO)₃ and iodine. Trifluoroacetic acid reacts with trans-[(MeO)₃P]₂Ru(CO)₃ to form cis-(CO)₂-trans-[(MeO)₃P]₂Ru(O₂CCF₃)₂. Treatment of trifluoroiodomethane with trans-[EtC(CH₂O)₃P]₂Ru(CO)₃ gives cis-(CO)₂-trans-[EtC(CH₂O)₃P]₂Ru(CF₃)l, whereas, trans-(PhPMe₂)₂Fe(CO)₃ gives an isomeric mixtures (CO)₂(PhPMe₂)₂Fe(CF₃)l. trans-L₂Ru(CO)₃(L = Ph₂PMe, or PhPMe₂) react with methylene chloride to give the respective dichlorides.