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The Reactions of R 2 Ga−GaR 2 and R 2 In−InR 2 [R = CH(SiMe 3 ) 2 ] with Protic Reagents: Substituent Exchange versus Cleavage of the Element−Element Bond
Author(s) -
Uhl Werner,
Graupner Rene,
Hahn Ingo,
Spies Thomas,
Frank Walter
Publication year - 1998
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199803)1998:3<355::aid-ejic355>3.0.co;2-h
Subject(s) - chemistry , dibenzoylmethane , medicinal chemistry , substituent , trimethylsilyl , bond cleavage , triple bond , dimer , ligand (biochemistry) , hydroxide , stereochemistry , organic chemistry , double bond , catalysis , biochemistry , receptor
Tetrakis[bis(trimethylsilyl)methyl]digallane(4) ( 1 ) with a Ga−Ga single bond and the corresponding diindane(4) 2 with an In−In single bond were treated with different protic reagents: tert ‐Butyl alcohol did not react with 1 at all, while phenol gave a mixture of unknown products, which could not be separated. The more acidic pentafluorophenol did not react as an acid, but C−F bonds were cleaved to form almost quantitatively the dimer (R 2 GaF) 2 5 , which was characterized by a crystal‐structure determination. Water and 1 yielded the dimeric dialkylgallium hydroxide 6 . The Ga−Ga bond was also cleaved by the reaction of 1 with durylthiophenol (duryl = 2,3,5,6‐tetramethylphenyl), which gave two main products: R 2 Ga(SDuryl) 7 and RGa(SDuryl) 2 8 . In contrast, the chelating acid dibenzoylmethane reacted by means of a substituent exchange, with the release of two equiv. of bis(trimethylsilyl)methane for each formula unit of 1 , to form 9 , in which the Ga−Ga bond is retained and each chelating 1,3‐diphenyl‐1,3‐propanedionato ligand is in a terminal position bonded to only one Ga atom, in more than 80% yield. The Ga−Ga bond is shortened [244.1(1) pm] compared to that in the starting compound tetraalkyldigallane(4) 1 . The In−In bond of diindane(4) 2 is, however, cleaved in a similar reaction with dibenzoylmethane, and only the fragmentation product dialkyl(1,3‐diphenyl‐1,3‐propanedionato)indium 10 could be isolated.