Department of Chemistry, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152-8551, Japan.
Dalton Trans. 2010 Jan 14(2):484-91. doi: 10.1039/b911082h. Epub 2009 Sep 2.
The reaction of 2,6-di-adamantyl-4-R-phenol (Ar(R)OH, R = Me, tBu) with nBuLi in THF gave good yields of the lithiated derivatives (Ar(R)O)Li(THF)2. Addition of 2 equiv. of (ArRO)Li(THF)2 to ZrCl4(THF)2 in THF afforded the base-free dichloride complexes (Ar(R)O)ZrCl2 (R = Me 1a, tBu 1b). The dibenzyl derivative (Ar(Me)O)2Zr(CH2Ph)2 2 was synthesized by addition of 2 equiv. of PhCH2MgCl to 1a in toluene. Reduction of the dichloride complexes 1a and 1b with KC8 in toluene led to the formation of the toluene-bridged dizirconium complexes [(Ar(R)O)2Zr]2(-6:6-C7H8) (R = Me 3a, tBu 3b). A similar reaction was carried out in benzene to produce the corresponding benzene-bridged analogue [(Ar(R)O)2Zr]2(mu-eta(6):eta(6)-C6H6) (R = Me 4a, tBu 4b). Treatment of 3a with 2 equiv. of 1-azidoadamantane (AdN3) in THF resulted in the release of toluene and N2, generating the monomeric imide complex (Ar(Me)O)2Zr(NAd)(thf) 5. When the analogous reaction was carried out in toluene, (Ar(Me)O)2Zr(AdNN=NNAd) 6 was obtained. Structures of (Ar(R)O)Li(THF)2, 1a, 2 and 5 were determined by X-ray crystallography.
2,6-二金刚烷基-4-R-苯酚（Ar(R)OH，R = Me，tBu）与 nBuLi 在 THF 中的反应生成了锂代衍生物（Ar(R)O）Li(THF)2，产率良好。向 ZrCl4(THF)2 在 THF 中的 2 当量（ArRO）Li(THF)2 中加入 2 当量（ArRO）Li(THF)2，得到无碱二氯配合物（Ar(R)O）ZrCl2（R = Me 1a，tBu 1b）。通过向 1a 中加入 2 当量的 PhCH2MgCl 在甲苯中合成了二苄基衍生物（Ar(Me)O）2Zr(CH2Ph)2 2。用 KC8 在甲苯中还原二氯配合物 1a 和 1b，得到了甲苯桥联双锆配合物[(Ar(R)O)2Zr]2(-6:6-C7H8)（R = Me 3a，tBu 3b）。在苯中进行类似的反应，生成相应的苯桥联类似物[(Ar(R)O)2Zr]2(mu-eta(6):eta(6)-C6H6)（R = Me 4a，tBu 4b）。在 THF 中用 2 当量的 1-叠氮金刚烷（AdN3）处理 3a，释放出甲苯和 N2，生成单体酰亚胺配合物（Ar(Me)O)2Zr(NAd)(thf) 5。当在甲苯中进行类似的反应时，得到（Ar(Me)O)2Zr(AdNN=NNAd) 6。（Ar(R)O）Li(THF)2、1a、2 和 5 的结构通过 X 射线晶体学确定。
