Dipalladium Complexes with Bridging Monoalkyl or Monophenyl
Silyl Ligands in the Solid State and in Solution
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Abstract
HexSiH<sub>3</sub>, PhSiH<sub>3</sub>, and PhSiClH<sub>2</sub> reacted with
[Pd(PCy<sub>3</sub>)<sub>2</sub>] to yield dipalladium complexes with
bridging silyl ligands: [{Pd(PCy<sub>3</sub>)}<sub>2</sub>(μ-HSiXR)<sub>2</sub>] (<b>1</b>, R = Hex, X = H; <b>2</b>, R = Ph,
X = H; <b>3</b>, R = Ph, X = Cl). The X-ray crystallographic
results displayed a typical bis(silyl)-bridged dinuclear structure
with an anti conformation of the substituents on the Si atom in the
solid state. Temperature-dependent NMR spectroscopic analyses of <b>1</b> and <b>2</b> revealed a dynamic <i>syn</i>–<i>anti</i> isomerization of the complex via exchange
of the bridging and nonbridging Si–H hydrogens in solution.
Complex <b>3</b> with bridging chloro(phenyl)silyl ligands did
not show such a dynamic behavior
