Reaction of ( = C₆H₃-2,6-(C₆H₂-2,4,6-Me₃)₂) with indium(I)chloride yields three m-terphenyl stabilized mixed-valent organoindium subhalides

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• 作者：Petra Vasko^a ; Akseli Mansikkamä ; ki^a ; James C. Fettinger^b ; Heikki M. Tuononen^a ; ^{heikki.m.tuononen@jyu.fi" class="auth_mail" title="E-mail the corresponding author} ; Philip P. Power^b ; ^{pppower@ucdavis.edu" class="auth_mail" title="E-mail the corresponding author}
• 关键词：Organoindium subhalides ; Mixed-valent compounds ; Molecular clusters ; X-ray crystallography ; DFT calculations
• 刊名：Polyhedron
• 出版年：2016
• 出版时间：8 January 2016
• 年：2016
• 卷：103
• 期：part_PA
• 页码：164-171
• 全文大小：1291 K

文摘

Indium(I)chloride reacts with LiAr^Me₆${\text{LiAr}}^{{\text{Me}}_6}$ (Ar^Me₆${\text{Ar}}^{{\text{Me}}_6}$ = C₆H₃-2,6-(C₆H₂-2,4,6-Me₃)₂) in THF to give three new mixed-valent organoindium subhalides. While the 1:1 reaction of InCl with LiAr^Me₆${\text{LiAr}}^{{\text{Me}}_6}$ yields the known metal-rich cluster In₈(Ar^Me₆${\text{Ar}}^{{\text{Me}}_6}$)₄ (1), the use of freshly prepared LiAr^Me₆${\text{LiAr}}^{{\text{Me}}_6}$ led to incorporation of iodide, derived from the synthesis of LiAr^Me₆${\text{LiAr}}^{{\text{Me}}_6}$, into the structures, to afford In₄(Ar^Me₆${\text{Ar}}^{{\text{Me}}_6}$)₄I₂ (2) along with minor amounts of In₃(Ar^Me₆${\text{Ar}}^{{\text{Me}}_6}$)₃I₂ (3). When the same reaction was performed in 4:3 stoichiometry, the mixed-halide compound In₃(Ar^Me₆${\text{Ar}}^{{\text{Me}}_6}$)₃ClI (4) was obtained. Further increasing the chloride:aryl ligand ratio resulted in the formation of the known mixed-halide species In₄(Ar^Me₆${\text{Ar}}^{{\text{Me}}_6}$)₄Cl₂I₂ that can also be obtained from the reaction of InCl with in situ   prepared LiAr^Me₆${\text{LiAr}}^{{\text{Me}}_6}$ in toluene. The new compounds 2 and 4 were characterized in the solid state by X-ray crystallography and IR spectroscopy, and in solution by UV/Vis and ¹H/¹³C{¹H} NMR spectroscopies. The structural characterization of 2 and 4 was supported by electronic structure calculations at the density functional level of theory which were also performed to rationalize the cluster-type bonding in 1.