Unexpected Outcome of the Reaction of [(COD)2Rh2(μ-OH)2] with TREAT HF or 50% HF. Peculiar Structural Features and Diminished Fluoride Basicity of [(R3P)4Rh2(μ-F)2] (R = i-Pr, Ph)

2004-06-21T00:00:00Z (GMT) by William J. Marshall Vladimir V. Grushin
The reaction of [(COD)Rh(μ-OH)]2 with TREAT HF (Et3N·3HF) or 50% HF in THF unexpectedly produced no Rh fluoride species but rather [Rh3(μ-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)4Rh2(μ-F)2] (X-ray) revealed a number of unexpected features pointing to a remarkably diminished basicity of the fluoro ligands.