Synthesis, Characterization, and Thermal Rearrangement of Zirconium Tetraazadienyl and Pentaazadienyl Complexes
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https://figshare.com/articles/dataset/Synthesis_Characterization_and_Thermal_Rearrangement_of_Zirconium_Tetraazadienyl_and_Pentaazadienyl_Complexes/2511241
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Reaction of the zirconium dichloro complex [Zr(N2TBSNpy)Cl2] (1) with 1 molar
equiv of ArNHLi (Ar = Mes, DIPP) yielded the zirconium imido complexes
[Zr(N2TBSNpy)(NDIPP)(py)] (2; N2TBSNpy = [(2-C5H4N)C(CH3){CH2NSi(CH3)2tBu}2]2–, DIPP = 2,6-diisopropylphenyl) and [Zr(N2TBSNpy)(NMes)(py)] (3; Mes = mesityl). The imido complexes are converted to the
tetraazadienido complexes [Zr(N2TBSNpy)(NDIPPN2NPh)] (4)
and Zr(N2TBSNpy)(NMesN2NPh)] (5) by addition of phenyl azide,
whereas the reaction of 2 or 3 with mesityl
azide gave the alternative product 7, in which the azide
is coupled with the CH activated ancillary tripod ligand. Reaction
of 1 molar equiv of trimethylsilyl azide or 1-adamantyl azide with
the previously reported hydrazinediido complex [Zr(N2TBSNpy)(NNPh2)(py)] (9) at ambient temperature resulted in the formation of the five-membered
zirconaacacycles [Zr(N2TBSNpy)(NTMSN3NPh2)] (10) and [Zr(N2TBSNpy)(NAdN3NPh2)] (11). Complex 11 was thermally
converted into the diazenido complex 12 via loss of 1
molar equiv of molecular N2. The direct formation of the
analogous side-on-bonded diazenido analogue 13 was observed
upon reaction of 9 with 1 equiv of mesityl azide at ambient
temperature. On the basis of 15N labeling and DFT modeling
(DFT(B3PW91/6-31 g(d))) a mechanism for the reaction pathway leading
to 12 and 13 is proposed.
创建时间：
2012-06-25
