Facile, aprotic degradation of η5-CpZrCl3•dme by ternary sodium/group 14 tert-butoxides: From η5-CpZrCl3•dme back to NaCp in two easy steps

CpZrCl3 center dot dme was treated with Na[El((OBu)-Bu-t)(3)], El = Ge, Sn, Pb, respectively. The addition of Na[Sn((OBu)-Bu-t)(3)] to CpZrCl3 center dot dme caused rapid cyclopentadienide loss and the equally rapid appearance of CpSnCl, half of which crystallized as the trinuclear complex {[ZrCl((OBu)-Bu-t)(3)](2)center dot CpSnCl}. Pristine CpSnCl reacted almost instantly with (NaOBu)-Bu-t to give NaCp and Na[Sn((OBu)-Bu-t)(3)], which co-crystallized as a coordination polymer. Na[Ge((OBu)-Bu-t)(3)] also displaced Cp from zirconium, but with a different product distribution, giving Cp2Ge, fac-[Ge(mu-(BuO)-Bu-t)(3)ZrCl((OBu)-Bu-t)(2)], and ZrCl((OBu)-Bu-t)(3). By contrast, Na[Pb((OBu)-Bu-t)(3)] only exchanged its tert-butoxide groups with zirconium to furnish CpZr((OBu)-Bu-t)(3) and PbCl2. The solid-state structures of {[ZrCl ((OBu)-Bu-t)(3)]2 center dot CpSnCl}, fac-[Ge(mu-(BuO)-Bu-t)(3)ZrCl((OBu)-Bu-t)(2)], and {NaCp center dot Na[Sn((OBu)-Bu-t)(3)]}(n) were determined. (C) 2011 Elsevier B. V. All rights reserved.