Organometalloidal derivatives of the transition metals

Treatment of ferrocenecarboxaldehyde with base at 0°C, lithium diisopropylamide (LDA) or n-butyllithium, followed by the addition of trimethylsilylcyanide, produced 1-(diisopropylamino)cyanomethylferrocene, FcCH(N{iPr}2(CN) (II) or 1-trimethyl-siloxy-n-pentylferrocene, FcCH(nBu)OSiMe3 (IIIa). The reaction of naphthaldehyde, NpCHO, with LDA/Me3SiCN led to formation of 1-(diisopropylamino)cyanomethylnaphthalene, NpCH{N(iPr)2}(CN) suggesting a general new synthesis for cyanoamines. The reaction of ferrocenecarboxaldehyde with Me3SiCN led to the expected silylether FcCH(CN)OSiMe3 (I). An alternative synthesis of ferrocenylmethylsilylethers, FcCH2OSiR3 (IV), involved the reaction of 1-ferrocenylmethanol with R3SiCl in the presence of pyridine. The basicity of the new silylethers III and IV is reported.