Utility of anhydrous neodymium nitrate as a precursor to extended organoneodymium nitrate networks.

Hydrated neodymium nitrates can be readily transformed to anhydrous ether solvates which react with cyclopentadienyl reagents to make organometallic nitrate complexes with variable degrees of oligomerization. Heating Nd(NO(3))(3)(H(2)O)(6) in tetrahydrofuran at reflux, removal of solvent, drying at 100 degrees C under high vacuum, and addition of hot THF generates Nd(NO(3))(3)(THF)(3), 1. Using dimethoxyethane, Nd(NO(3))(3)(DME)(2), 2, can be obtained similarly. Addition of NaC(5)Me(5) to 1 generates (C(5)Me(5))Nd(NO(3))(3)(THF)Na(THF)(x)complexes which crystallize as ([(C(5)Me(5))(NO(3))(2)Nd(THF)(micro-NO(3))](2)Na(THF)(4))[Na(THF)(6)], 3, or [(C(5)Me(5))Nd(THF)(mu-NO(3))(3)Na(THF)(2)](n), 4, depending on the conditions. The trimetallic Nd(2)Na unit in 3 forms an extended system in 4 via bridging nitrates. Addition of KC(5)Me(5) and 18-crown-6 to 1 generates another extended complex [(C(5)Me(5))Nd(THF)(NO(3))(mu-NO(3))(2)K(18-crown-6)](n), 5, in which an 18-crown-6 ligated potassium links neodymium centers via two bridging nitrates and an agostic interaction between a C(5)Me(5) methyl group and potassium.