Synthesis and molecular structures of the 1,2-dihalogen derivatives of Ga(II) and In(II), [{GaI(Ar^Me6)}₂], [{InCl(Ar^Me6)}₂]₂, [{InI(Ar^Me6)}₂]₂, and [{In₄Cl<

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• 作者：Oracio Serrano ; James C. Fettinger ; Philip P. Power ; ^{pppower@ucdavis.edu}
• 关键词：Terphenyl ; Subvalent gallium ; Indium ; X-ray crystallography
• 刊名：Polyhedron
• 出版年：2013
• 出版时间：13 July, 2013
• 年：2013
• 卷：58
• 期：Complete
• 页码：144-150
• 全文大小：1398 K

文摘

The reaction of LiAr^Me6 [Ar^Me6C₆H₃-2,6(C₆H₂-2,4,6-Me₃)₂] with InCl, [In(InI₄)], InCl in the presence of LiI, or ¡®GaI¡¯ in toluene solution resulted in the isolation of the 1,2-diaryl-1,2-dihalogen derivatives [{InCl(Ar^Me6)}₂]₂ (1), [{InI(Ar^Me6)}₂]₂ (2), [{In₄Cl₂I₂(Ar^Me6)₄}] (3), and [{GaI(Ar^Me6)}₂] (4). The indium derivatives 1-3 were isolated as tetrametallic complexes formed via the almost symmetric bridging by four halides of two In-In bonded, Ar^Me6In-InAr^Me6 moieties. In 1, the In₄Cl₄ core features almost parallel In-In units, linked by four almost symmetrically bridging chlorides. This yields a structure formed from two folded In₂Cl₂ rings, and two six-membered In₄Cl₂ boat-shaped rings that have common In-Cl edges. The structures of 2 and 3 also feature two Ar^Me6InInAr^Me6 units bridged by four halides. However, there is a large torsion angle between the two In-In vectors, so that the In₄I₄ (2) and In₄Cl₂I₂ (3) cores are formed from four five-membered In₃I₂ (2) or In₃ClI (3) rings. Compound 4 has a simple Ga-Ga bonded dimeric structure, in which the gallium atoms are three coordinated, being bonded to each other as well as to an iodine and an Ar^Me6 ligand. All the compounds were characterized by ¹H and ¹³C {¹H} NMR spectroscopy, and by X-ray crystallography. The structural differences between the gallium and indium derivatives is probably a result of the larger size and greater Lewis acidity of the indium centers.