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Synthesis of B/Ga and B/In Heteronuclear Bidentate Lewis Acids: Formation of Intramolecular pi-arene-gallium(III) and -indium(III) Complexes

Synthesis of B/Ga and B/In Heteronuclear Bidentate Lewis Acids: Formation of Intramolecular pi-arene-gallium(III) and -indium(III) Complexes

Marcus Schulte, François P Gabbaï

Chemistry. 2002 Aug 16;8(16):3802-7.

PMID: 12203306

Abstract:

Reaction of 1,8-dilithionaphthalene x TMEDA (TMEDA=tetramethylethylenediamine) with dimesitylboron fluoride in diethyl ether followed by treatment with THF affords the Li(THF)(4) salt of dimesityl-1,8-naphthalenediylborate (1). Compound 1-Li(THF)(4) undergoes a ring-opening reaction with trimethyltin chloride to afford high yields of 1-(dimesitylboron)-8-(trimethyltin)naphthalenediyl (2), a compound in which a boryl and a stannyl moiety coexist at the peri positions of a naphthalene core. Compound 2 has been characterized by multinuclear NMR spectroscopy, elemental analysis, and X-ray single-crystal analysis which reveal the existence of a sterically crowded structure. Compound 2 is a useful starting material for the synthesis of other heteronuclear naphthalene derivatives. Thus, the transmetalation reaction of 2 with GaCl(3) or InCl(3) in THF results in high yields of 1-(dichlorogallium)-8-(dimesitylboron)naphthalenediyl (3) and 1-(dichloroindium)-8-(dimesitylboron)naphthalenediyl (4), respectively. These unprecedented boron/gallium and boron/indium heteronuclear bidentate Lewis acids have been characterized by multinuclear NMR spectroscopy, elemental analysis, and X-ray single-crystal analysis. Owing to the presence of a short contact between the ipso-carbon atom of a mesityl group and the heavy Group 13 element (C(ipso)bondGa 2.279(4) A for 3, C(ipso)bondIn 2.442(6) A for 4), compounds 3 and 4 are best described as intramolecular pi-arene complexes and are the first examples of such complexes. As shown by (1)H and (13)C NMR spectroscopy, this pi interaction subsists in solution.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP436599	Dimesitylboron fluoride		436-59-9	Price

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