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Updated: Aug 14, 2026

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Thermodynamics, kinetics, and mechanism of the reversible formation of oxorhenium(VII) catecholate complexes
K A Brittingham1, J H Espenson
1Ames Laboratory and the Department of Chemistry, Iowa State University of Science and Technology, Ames, Iowa 50011, USA.
Abstract:
Mononuclear Re(V) compounds MeReO(mtp)NC(5)H(4)X, 3, where mtpH(2) is 2-(mercaptomethyl)thiophenol have been prepared from the monomerization of [MeReO(mtp)](2) by pyridines with electron-donating substituents in the para or meta position; X = 4-Me, 4-Bu(t), 3-Me, 4-Ph, and H. Analogous compounds, MeReO(edt)N(5)H(4)X, 4, edtH(2) = 1,2-ethanedithiol, were prepared similarly. The equilibrium constants for the reaction, dimer + 2Py = 2M-Py, are in the range (2.5-31.6) x 10(2) L mol(-1). Both groups of monomeric compounds react with quinones (phenanthrenequinone, PQ, and 3,5-tert-butyl-1,2-benzoquinone, DBQ), displacing the pyridine ligand and forming Re(VII) catecholate complexes MeReO(dithiolate)PCat and MeReO(dithiolate)DBCat. With PQ, the reaction MeReO(dithiolate)Py + PQ = MeReO(dithiolate)PCat + Py is an equilibrium; values of K(Q) for different Py ligands lie in the ranges 9.2-42.7 (mtp) and 3.2-11.2 (edt) at 298 K. These second-order rate constants (L mol(-1) s(-1)) at 25 degrees C in benzene were obtained for the PQ reactions: k(f) = (5.3-15.5) x 10(-2) (mtp), (6.6-16.4) x 10(-2) (edt); k(r) = (3.63-5.71) x 10(-3) (mtp), (14.7-22.0) x 10(-3) (edt). The ranges in each case refer to the series of pyridine ligands, the forward rate constant being the largest for C(5)H(5)N, with the lowest Lewis basicity. The reactions of MeReO(dithiolate)Py with DBQ proceed to completion. Values of k(f)/L mol(-1) s(-1) fall in a narrow range, 4.02 (X = Bu(t)) to 8.4 (X = H) with the dithiolate being mtp.
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