Synthesis and structures of zirconium amide-iodide complexes

Zirconium amide-iodide complexes were synthesized for possible use as chemical vapor deposition precursors to zirconium nitride films. The series of six complexes Zr(NR(2))(4-n)I(n)(R = Me or Et; n = 1-3) was prepared by reacting ZrI(4) and Zr(NR(2))(4) in hot toluene. X-ray crystallographic analyses were performed for Zr(NMe(2))(3)I, Zr(NEt(2))(2)I(2), and Zr(NEt(2))I(3). In the solid state, Zr(NMe(2))(3)I and Zr(NEt(2))(2)I(2) are the discrete dimers Zr(NMe(2))(2)I(mu-NMe(2))](2) and Zr(NEt(2))(2)I(mu-I)](2), and Zr(NEt(2))I(3) is the polymer of dimers (Zr(NEt(2))I(2)(mu-I)](2))(n). In solution, Zr(NEt(2))(3)I is proposed to be monomeric on the basis of NMR data and a molecular weight determination. The complex Zr(NEt(2))(3)I is the most promising precursor candidate because of its physical properties.