Synthesis, structure, and reactivity of organometallic lanthanide-dizirconium nonaisopropoxide complexes

The feasibility of using [Zr-2(OiPr)(9)](-) as a stabilizing, ancillary lig and in organometallic lanthanide complexes has been examined. The dizirconi um nonaisopropoxide (dzni) ligand has been found to be compatible with cycl opentadienyl and cyclooctatetraenyl reagents and enhances the solubility of divalent lanthanide organometallic species in comparison with (C5H5)(-) an alogues. [{[Zr-2(OiPr)(9)]LnI}(2)] reacts with NaC3H5 to form the hexane-so luble divalent lanthanide complexes [{Zr-2(oiPr)(9)}Ln(C5H5)] (1: Ln = Sm; 2: Ln=Yb). Complex I is the first reported soluble (C5H5)(-) complex of Sm- II. [{[Zr-2(OiPr)(9)]LnI}(2)] reacts with K2C8H8 to form the bimetallic Ln( II) complexes [{[Zr-2(oiPr)(9)]Ln}(2)(C8H8)] (3: Ln = Sm; 4: Ln = Yb), whic h are also hexane-soluble. Complex 3 reacts with 1,3,5,7-C8H8 to form hexan e-soluble [{Zr-2(OiPr)(9)}Sm(C8H8)], 5, in a manner analogous to the reduct ion of C8H8 by [{(C5Me5)Sm}(2)(C8H8)]. In all these complexes, the monoanio nic [Zr-2(OiPr)(9)](-) unit is attached to the lanthanide metal in a tetrad entate fashion.