Intramolecular and Intermolecular Ligand Exchange in Trifluorophosphinerhodium Complexes of Di-tert-butylacetylene. Rotation of Trifluorophosphine Groups about a Rhodium-Rhodium Double Bond

M. A. Bennett, R. N. Johnson, T. W. Turney

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Abstract

Octakis(trifluorophosphine)dirhodium, Rh2(PF3)8, reacts with di-tert-butylacetylene, t-Bu2C2, to give a yellow, crystalline complex Rh2(PF3)5(t-Bu2C2). This is believed to contain a bridging acetylene moiety lying over and perpendicular to Rh(PF3)3 and Rh(PF3)2 groups which are joined by a rhodium-rhodium double bond. 19F NMR spectra in the temperature range 24-116° show that the PF3 groups on each rhodium atom undergo intramolecular exchange with identical activation energies but without exchanging between the rhodium atoms, i.e., the ligands rotate about the metal-metal double bond. The free energy of activation ΔG is estimated from line shape analysis to be 15.1 ± 0.5 kcal/mol, being independent of temperature. The complex Rh2(PF3)5(t-Bu2C2) reversibly adds PF3 to give Rh2(PF3)6(t-Bu2C2) which undergoes both intramolecular and intermolecular exchange of PF3. The free energy of activation ΔG for the intramolecular process, estimated as 13.3 kcal/mol, is considerably higher than the values found for other Rh2(PF3)6(ac) complexes, probably owing to steric hindrance by the bulky tert-butyl groups. This feature is probably also responsible for the relative ease of intermolecular PF3 exchange in Rh2(PF3)6(t-Bu2C2) and for the stability of Rh2(PF3)5(t-Bu2C2).

Original languageEnglish
Pages (from-to)111-114
Number of pages4
JournalInorganic Chemistry
Volume15
Issue number1
DOIs
Publication statusPublished - 1 Jan 1976
Externally publishedYes

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