ic0521731_si_001.cif (148.48 kB)

Insertion of the Ga(I) Bis-imidinate Ga(DDP) into the Metal Halogen Bonds of Rh(I) Complexes. How Electrophilic Are Coordinated Ga(DDP) Fragments?

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posted on 03.04.2006, 00:00 by Andreas Kempter, Christian Gemel, Ned J. Hardman, Roland A. Fischer
The reactivity of Ga(DDP) (DDP = 2-((2,6-diisopropylphenyl)amino-4-((2,6-diisopropylphenyl)imino)-2-pentene) towards the rhodium−chloride bonds of [RhCl(PPh3)3] and [RhCl(COE)2]2 (COE = cyclooctene) is investigated. Reaction of the first complex leads to [(Ph3P)2Rh{Ga(DDP)}(μ-Cl)] (1), exhibiting a chloride bridging the gallium and the rhodium atoms, whereas the second complex leads to a full insertion of the Ga(DDP) ligand into the Rh−Cl bond giving [(COE)(benzene)Rh{(DDP)GaCl}] (2) on coordination of the solvent C6H6. Compounds 1 und 2 readily react with the halide abstracting reagent Tl[BArF] (BArF = B[3,5-(CF3)2C6H3]4), yet the products could not be isolated and characterized because of their lability. The Au(I) complex [{(DDP)Ga}Au{Ga(DDP)}Cl] reacts with Na[BArF] giving the linear, symmetric cationic complex [{(DDP)Ga·THF}2Au][BArF] (3·2THF), exhibiting two THF molecules coordinated to the Ga(DDP) moieties.