31906-88-4Relevant academic research and scientific papers
The kinetics and mechanism of substitution reactions of some osmium(II)-dinitrogen complexes
Maples, Peter K.,Basolo, Fred,Pearson, Ralph G.
, p. 765 - 770 (2008/10/08)
The rate of molecular nitrogen substitution of Os(N2)X2L3 (L = P(CH3)2C6H5, P(C2H5)2C6H5; X = Cl, Br) and Os(N2)X2L2L′ (L = P(CH3)2C6H5; L′ = P(OCH3)2C6H5; X = Cl, Br) by phosphorus ligands has been studied in toluene by ir spectrophotometry. The reactions are first order in complex concentration and independent of ligand concentration. The ranges of the activation parameters for these reactions are ΔH* = 27-34 kcal/mol and ΔS* = 9-17 eu. These results are compatible with a dissociative (SN1) mechanism. Evidence is presented for ligand exchange in the reactions between Os(N2)X2L3 compounds and certain phosphites. The effect of structural variation on the rate of nitrogen substitution is discussed and a comparison between the dinitrogen compounds studied and their carbon monoxide analogs is made.
