EPR Study of the Low-Spin [d3; S =/2], Jahn−Teller-Active, Dinitrogen Complex of a Molybdenum Trisamidoamine

Abstract

The first EPR study of the trisamidoamine complex, [Mo]N₂, where [Mo] = Mo(III)[HIPTN₃N] and HIPT = [3,5-(2,4,6-i-Pr₃-C₆H₂)₂C₆H₃NCH₂CH₂]₃N^3-, reveals that this low-spin (S = ¹/₂) [d³] complex exhibits a ²E state that undergoes a pseudo Jahn−Teller distortion in the adiabatic limit, modified by interactions with the solvent, and analysis gives approximate values of interaction energies. The experiments establish that [Mo]N₂ exhibits the low-spin [e³] electronic configuration, not [a²e¹], with the a(z²) antibonding orbital substantially higher in energy than the e[xz, yz] orbitals.