Determination of structural features of electrogenerated trans-[MoCl(NMe)(Ph2PCH2CH2PPh2)2]2+ by multinuclear electron paramagnetic resonance and electron nuclear double resonance spectroscopy and comparison of interatomic distances with those measured by X-ray analysis of the parent monocation

Abstract

The 17-electron dication trans-[MoCl(NMe)(Ph₂PCH₂CH₂PPh₂)₂]²⁺ was electrogenerated as a stable solution species in a trifluoroacetic acid electrolyte and its structure deduced by analysis of multinuclear e.p.r. and electron nuclear double resonance spectra. Certain interatomic distances within this molybdenum(IV) dication were calculated from the magnitude of anisotropic dipolar interactions obtained from field-dependent ENDOR frequency-shift measurements and comparisons made with distances measured by X-ray analysis of the parent monocation. It is concluded that the {MoNMe} group in the 17-electron product retains the geometric configuration of its 18-electron precursor.