Abstract
The synthesis, characterization, and reactivity of novel carbogerma[2]ferrocenophanes, (η-C5Me4)Fe(η-C5H4)CH2GeR2, 11 (a, R = Ph; b, R = Me), and carbostanna[2]ferrocenophanes, (η-C5Me4)Fe(η-C5H4)CH2SnR2, 12 (a, R = tBu; b, R = Mes; c, R = Me), are reported. Compounds 11a,b and 12a−c were isolated as orange crystals from the reaction of (η-C5Me4)Fe(η-C5H4Li)CH2Li·xTMEDA with Cl2ER2 (E = Ge, R = Ph, Me or E = Sn, R = tBu, Mes, Me) and were characterized by 1H, 13C, and 119Sn NMR, UV/vis, MS, and in representative cases elemental analysis. X-ray diffraction analysis of these species revealed structures possessing moderate ring-tilt with values in the range α = 10.99(2)−11.81(5)° for 11a,b and α = 6.64(2)−7.5(1)° for 12a−c. The presence of a small or moderate degree of ring-strain was further substantiated through the observation of only a small (ca. 25−30 nm) bathochromic shift in the UV/vis absorption maxima when compared to pentamethylferrocene. Attempts to induce thermal ring-opening polymerization (ROP)...
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