Germanium-containing ferrocenes and ferrocenophanes. Potential precursors for ring-opening polymerizations and ‘germaferrocenes’

The new germanium-containing ferrocene and ferrocenophane derivatives (2,3,4,5-tetramethylbuta-1,3-dien-1,4-diyl)-germa-[1]ferrocenophane ( 2 ), 2-(2,3,4,5-tetramethylbuta-1,3-dien-1,4-diyl)-1,3-dithia-2-germa-[3]ferrocenophane ( 3 ), 1,1′-bis(1-ethoxy-2,3,4,5-tetramethyl-1-germacyclopenta-2,4-dienyl)-ferrocene ( 6 ), 1,3-bis(2,3,4,5-tetramethylbuta-1,3-dien-1,4-diyl)-1,3-digerma-2-oxo-[3]ferrocenophane ( 7 ), 1,1′-bis(1-hydrido-2,3,4,5-tetramethyl-1-germacyclopenta-2,4-dienyl)-ferrocene ( 8 ) and 1,2-bis(2,3,4,5-tetramethylbuta-1,3-dien-1,4-diyl)-digerma-[2]ferrocenophane ( 9 ) have been prepared starting from the dichlorogermol 1. The synthesis of the known ferrocenophanes dichloro-(ferrocene-1,1′-dithiolato)-germane ( 10a ) and dichloro-(ferrocene-1,1′-dithiolato)-stannane ( 10b ) was improved. X-ray crystal structural studies of 2 (C 18 H 20 FeGe, a =10.907(4), b =11.040(4), c =13.771(5) Å, β =110.87°, monoclinic, C 2/ c (No. 15), Z=4), 3 (C 18 H 20 FeGeS 2, a =8.104(3), b =8.593(4), c =13.177(6) Å, α =70.79(4), β =77.56(3), γ =85.80(3) Å triclinic, P 1̄ (No. 2), Z =2), 7 (C 26 H 32 FeGe 2 O, a =18.95(2), b =8.557(6), c =16.69(6) Å, β =110.65(6)°, monoclinic, C 2/ c (No. 15), Z =4), 9 (C 26 H 32 FeGe 2, a =11.209(6), b =10.839(5), c =19.819(10) Å, β =92.89(2), γ =90°, monoclinic, P 2 1 / n (No. 14), Z =4), 10a (C 10 H 8 FeGeS 2, a =10.873(5), b =7.417(4), c =16.415(10) Å, orthorhombic, Pca 2 1 (No. 29), Z=4), 12a (C 20 H 16 Fe 2 GeS 4, a =7.459(4), b =10.921(5), c =23.552(12) Å, orthorhombic, Pbcn (No. 60), Z=4) and 12b (C 20 H 16 Fe 2 SnS 4, a =7.484(4), b =10.953(6), c =23.917(12) Å, orthorhombic, Pbcn (No. 60), Z =4) and cyclovoltammetric characterizations for all ferrocene-containing compounds have been carried out.