Preparation and Thermal Reaction of Tetrastannapalladacyclopentane. Sn−Sn Bond Formation and Cleavage
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posted on 2010-08-23, 00:00 authored by Makoto Tanabe, Masaya Hanzawa, Kohtaro OsakadaReaction of H<sub>2</sub>SnPh<sub>2</sub> with [Pd(dmpe)<sub>2</sub>]<sub><i>n</i></sub> (<i>n</i> = 1 or 2; dmpe
= 1,2-bis(dimethylphosphino)ethane) in 4:1 ratio produces a tetrastannapalladacyclopentane,
[Pd(SnPh<sub>2</sub>SnPh<sub>2</sub>SnPh<sub>2</sub>SnPh<sub>2</sub>)(dmpe)] (<b>1</b>), via dehydrogenative Sn−Sn
bond formation. Heating of <b>1</b> in toluene at 70 °C
cleaves the Sn−Sn bonds, which is accompanied by migration
of Ph groups, to form a bis(triphenylstannyl)palladium complex, [Pd(SnPh<sub>3</sub>)<sub>2</sub>(dmpe)] (<b>2</b>). A similar reaction
of H<sub>2</sub>SnPh<sub>2</sub> with [Pd(PCy<sub>3</sub>)<sub>2</sub>] yields a dipalladium(I) complex with bridging diphenylstannyl ligands,
[{Pd(PCy<sub>3</sub>)}<sub>2</sub>(μ-η<sup>2</sup>-HSnPh<sub>2</sub>)<sub>2</sub>] (<b>3</b>).
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