SYNTHESIS AND STRUCTURE OF A ZIRCONIUM DINITROGEN COMPLEX WITH A SIDE-ON BRIDGING N-2 UNIT

Reduction of Zr(O-2, 6-Me2C6H3)Cl-2[N(SiMe2CH2PPr2i)(2)] with sodium a malgam under dinitrogen yields the dinuclear zirconium dinitrogen comp lex {[((Pr2PCH2SiMe2)-P-i)(2)N]Zr(O-2, 6-Me2C6H3)}(2)(mu-eta(2):eta(2) -N-2). Solid state structural analysis shows that the dinitrogen unit is bound in a side-on mode of coordination with the N-N bond distance at 1.528(7) Angstrom; resonance Raman spectra show a band at 751 cm(-1 ) for v(N-N), which is consistent with this very long bond. In additio n, the N-2 ligand is hinged slightly so that the Zr-2(mu-eta(2):eta(2) -N-2) core adopts a flattened butterfly shape rather than a completely planar core as found in other related systems. Other Zr(IV) precursor s of the general formula ZrCl2X[N(SiMe2CH2PPr2i)(2)] (X = OBut, OCHPh2 , NPh2) either decompose upon reduction under N-2 or produce mixtures of products.