Synthesis, reactivity, and some photochemistry of ortho-N,N-dimethylaminomethyl substituted aryl and ferrocenyl pentamethylcyclopentadienyl dicarbonyl iron complexes

•New pentamethylcyclopentadienyl dicarbonyl iron complexes are synthesized.•The parent alkoxy-substituted complexes are obtained by quaternization/alcoholysis.•Photolytic displacement of carbonyl ligands is achieved to form chelated complexes.

Ortho-lithiated N,N-dimethylaminomethyl ferrocene and benzyldimethylamine react with Cp*Fe(CO)2I to give the new complexes ((Cp*Fe(CO)2)-2-(CH2NMe2)C5H3)Fe(Cp) and Cp*Fe(CO)2-C6H4(o-CH2NMe2). Access to a wide variety of alkoxy-substituted complexes ((Cp*Fe(CO)2)-2-(CH2OR)C5H3)Fe(Cp) can be easily achieved by tandem quaternization/alcoholysis of ((Cp*Fe(CO)2)-2-(CH2NMe2)C5H3)Fe(Cp). Preliminary results show that chelated complexes can be obtained by displacement of one of the carbonyl ligands by photolysis. Crystal structures of ((Cp*Fe(CO)2)-2-(CH2NMe2)C5H3)Fe(Cp), ((Cp*Fe(CO)2)-2-(CH2OR)C5H3)Fe(Cp) (R = Ph, Bz, CHPh2 and d-menthyl) and [Cp*Fe(CO)2-C6H4(o-CH2NMe2)][I] are reported.

((Cp*Fe(CO)2)-2-(CH2NMe2)C5H3)Fe(Cp) and Cp*Fe(CO)2-C6H4(o-CH2NMe2) are synthesized from Cp*Fe(CO)2I and ortho-lithiated N,N-dimethylaminomethyl ferrocene or benzyldimethylamine. Alkoxy-substituted complexes ((Cp*Fe(CO)2)-2-(CH2OR)C5H3)Fe(Cp) can be easily obtained by tandem quaternization/alcoholysis of ((Cp*Fe(CO)2)-2-(CH2NMe2)C5H3)Fe(Cp). Photolytic displacement of one of the carbonyl ligands of Cp*Fe(CO)2-C6H4(o-CH2NMe2) yield the corresponding chelated complex.Figure optionsDownload full-size imageDownload as PowerPoint slide