Elucidating the mechanism of the halide-induced ligand rearrangement reaction

Hyojong Yoo, Mari S. Rosen, Aaron M. Brown, Michael J. Wiester, Charlotte L. Stern, Chad A. Mirkin*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

10 Scopus citations


The formation of heteroligated Rh I complexes containing two different hemilabile phosphinoalkyl ligands, (κ 2-Ph 2PCH 2CH 2S-Aryl)(κ 1-Ph 2PCH 2CH 2O-C 6H 5)RhCl, through a halide-induced ligand rearrangement (HILR) reaction has been studied mechanistically. The half-life of this rearrangement reaction depends heavily on the Rh I precursor used and the chelating ability of the phosphinoalkyl thioether (PS) ligand, while the chelating ability of the phosphinoalkyl ether (PO) ligand has less of an effect. An intermediate complex which contains two PO ligands, (nbd)(κ 1-Ph 2PCH 2CH 2O-C 6H 5) 2RhCl (nbd = norbornadiene), converts to (nbd)(κ 1-Ph 2PCH 2CH 2O-C 6H 5)RhCl resulting in a free PO ligand. The free PO ligand can then react with a homoligated PS complex [(κ 2-Ph 2PCH 2CH 2S-Aryl) 2Rh] +Cl - producing the heteroligated product. The PS ligand generated during the reaction pathway can be trapped by the monoligated PO complex (nbd)(κ 1-Ph 2PCH 2CH 2O-C 6H 5)RhCl, leading to the formation of the same heteroligated product. In this study, some of the key intermediates and reaction steps underlying the HILR reaction have been identified by variable temperature 31P{ 1H} NMR spectroscopy and in two cases by single-crystal X-ray diffraction studies. Significantly, this work provides mechanistic insight into the HILR process, which is a key reaction used to prepare a large class of highly sophisticated three-dimensional metallosupramolecular architectures and allosteric catalysts.

Original languageEnglish (US)
Pages (from-to)11986-11995
Number of pages10
JournalInorganic chemistry
Issue number21
StatePublished - Nov 5 2012

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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