The proton relaxation of methyl cyanide in the presence of Ni(II) ions, as studied by spin-echo techniques

Abstract

The proton relaxation times (T ₁ and T ₂) of methyl cyanide, in the presence of Ni(II) ions, have been measured as a function of temperature and frequency by spin-echo techniques. The observed decay times (T ₂†) have also been measured as a function of the separation, t _ep, between the pulses in a Carr-Purcell train of echos. The results obtained in the limit of long pulse separation have been fitted to existing theories. The rotational correlation time of the Ni/MeCN complex, τ _R , the electron spin relaxation time, τ _S , and the distance of closest approach of the protons to the nickel have been estimated from the results. In addition the scalar coupling constant, the exchange rate τ _B and the activation energies for τ _B , τ _S and τ _R have been evaluated. The chemical exchange parameters obtained differ significantly from those obtained by previous workers. There is evidence from the pulse dependence experiments that the complex is a distorted octahedron.