Substitution reactions on sterically hindered square-planar trans-[NiBr(R)(PR′3)2](R = aryl) complexes. Effects of the substituents of the aryl ligand

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Abstract
Substitution reactions of sterically hindered trans-[NiBr(R)(PPh3)2] complexes (R = C6Cl5, C6F5,C6H2Me3-2,4,6, C6HCl4-2,3,5,6, C6HCl4-2,3,4,6, C6HCl4-2,3,4,5, C6H2Cl3-2,3,4, C6H3Cl2-2,4, or C6H4Cl-2) and of trans-[NiBr(R)(PR′3)2](PR′3= PEtPh2 or PMePh2; R = C6Cl5 C6F5, C6H2Me3-2,4,6, or C6H2Cl3-2,3,4) have been studied in acetone solution. The reaction rates obey the well established two-term rate law kobs=kS+kan[anion] and seem to be solely controlled by steric factors; namely, the existence of one or two substituents on the R ligand, in an ortho position with respect to the Ni–C bond. The different donor ability of the ligand might be considered only for R = C6H2Me3-2,4,6. The effects of the para and meta chloro substituents of the R ligand on the reaction rates are negligible. Steric strain in the molecule, as a whole, is also considered by studying the effect of a decrease in the phosphine size on the reaction rate.

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