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)
作者:William J. Marshall、Vladimir V. Grushin
DOI:10.1021/om049813c
日期:2004.6.1
The reaction of [(COD)Rh(mu-OH)](2) with TREAT HIP (Et,9N-3HF) or 50% HF in THF unexpectedly produced no Rh fluoride species but rather [Rh-3(mu-OH)(2)(COD)(2)]HF2 (1), in high yield. Single-crystal and powder X-ray diffraction studies established the structure of 1 and confirmed that the product was homogeneous in bulk. The structure of [(i-Pr3P)(4)Rh-2(mu-F)(2)] (X-ray) revealed a number of unexpected features pointing to a remarkably diminished basicity of the fluoro ligands.