Kinetics, equilibrium, and computational study on the monomerization reaction of {CH3ReVO(pdt)}2 dimer with monodentate ligands

• Published in: Journal of organometallic chemistry 2023-12, Vol.1002, p.122907, Article 122907
• Main Authors: Ibdah, Abdellatif, Hijazi, Ahmed, Hamad, Nour Bany
• Format: Article
• Language: English
• Subjects: Kinetics; Monomerization reaction; Rhenium(v) dimer
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/j.jorganchem.2023.122907

The monomerization reaction of {MeReO(pdt)}2 dimer (the pdt is 1,3-propanedithiolate) with monodentate ligand has been studied experimentally:{MeReO(pdt)}  + 2 L ⇌ 2 MeReO(pdt)L and L is a monodentate ligand presented in Figure 1. No monomerization reaction have been observed with the indazole and diphenyl sulfides, and 2-methylpyridne. For the 2-methylpyridne case, the no reaction was observed because of the steric effect of the methyl group at the ortho position prevent the nitrogen from coordination. But the phosphines and pyridines derivatives monomerize the dimer. The rate law is given by ν = (ka[L] + kb [L]2) {MeReO(pdt)2} for ligands 1 to 4 in Table 1 and the rate law is ν = kb [L]2 {MeReO(pdt)2} for ligands 6 to 8 in Table 1. The equilibrium constant of the same reaction has been also evaluated. The rate constant (k) and the equilibrium constant (Keq) values correlate well with the basicity of the ligand. The reaction constant (ρ) is -4.9 and -1.3 for pyridine and phosphine, respectively, obtained from Hammett correlation with σ. The computational study on I1 and I2 intermediates (Scheme 3) shows that these intermediates are not plausible intermediates as previously proposed1, 2. These results are attributed to the high angle strain on the bridging sulfur that prevent the formation of the I1 and I2 intermediates and the reaction proceed through different intermediates (I3 and Ia Scheme 4). Therefore, the proposed mechanism is modified to accommodate the computational results. [Display omitted]