Synthesis and structure of a zirconium dinitrogen complex with a side-on bridging N2 unit

被引:53
作者
Cohen, JD
Fryzuk, MD
Loehr, TM
Mylvaganam, M
Rettig, SJ
机构
[1] Univ British Columbia, Dept Chem, Vancouver, BC V6T 1Z1, Canada
[2] Oregon Grad Inst Sci & Technol, Dept Biochem & Mol Biol, Portland, OR 97291 USA
关键词
D O I
10.1021/ic9709786
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Reduction of Zr(O-2, 6-Me2C6H3)Cl-2[N(SiMe2CH2PPr2i)(2)] with sodium amalgam under dinitrogen yields the dinuclear zirconium dinitrogen complex {[((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 addition, 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) precursors of the general formula ZrCl2X[N(SiMe2CH2PPr2i)(2)] (X = OBut, OCHPh2, NPh2) either decompose upon reduction under N-2 or produce mixtures of products.
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页码:112 / 119
页数:8
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