Unexpected Outcome of the Reaction of [(COD)<sub>2</sub>Rh<sub>2</sub>(μ-OH)<sub>2</sub>] with TREAT HF or 50% HF. Peculiar Structural Features and Diminished Fluoride Basicity of [(R<sub>3</sub>P)<sub>4</sub>Rh<sub>2</sub>(μ-F)<sub>2</sub>] (R = <i>i</i>-Pr, Ph)<sup>†</sup>

2004-06-21T00:00:00Z (GMT) by William J. Marshall Vladimir V. Grushin
The reaction of [(COD)Rh(μ-OH)]<sub>2</sub> with TREAT HF (Et<sub>3</sub>N·3HF) or 50% HF in THF unexpectedly produced no Rh fluoride species but rather [Rh<sub>3</sub>(μ-OH)<sub>2</sub>(COD)<sub>2</sub>]HF<sub>2</sub> (<b>1</b>), in high yield. Single-crystal and powder X-ray diffraction studies established the structure of <b>1</b> and confirmed that the product was homogeneous in bulk. The structure of [(<i>i</i>-Pr<sub>3</sub>P)<sub>4</sub>Rh<sub>2</sub>(μ-F)<sub>2</sub>] (X-ray) revealed a number of unexpected features pointing to a remarkably diminished basicity of the fluoro ligands.