hide
Free keywords:
-
Abstract:
The reaction of 2 equiv of the bulky ligand N,N‘-bis(3,5-di-tert-butylphenyl)-1,2-phenylenediamine, H2[3LPDI], excess triethylamine, and 1 equiv of M(CH3CO2)2·4H2O (M = Ni, Co) in the presence of air in CH3CN/CH2Cl2 solution yields violet-black crystals of [NiII(3LISQ)2] CH3CN (1) or violet crystals of [Co(3L)2] (3). By using Pd(CH3CO2)2 as starting material, green-blue crystals of [PdII(3LISQ)2]·CH3CN (2) were obtained. Single-crystal X-ray crystallography revealed that 1 and 3 contain (pseudo)tetrahedral neutral molecules [M(3L)2] (M = Ni, Co) whereas in 2 nearly square planar, neutral molecules [PdII(3LISQ)2] are present. Temperature-dependent susceptibility measurements established that 1 and 2 are diamagnetic (S = 0) whereas 3 is paramagnetic with an S = 3/2 ground state. It is shown that 1 contains two π radical benzosemiquinonate(1−)-type monoanions, ((3LISQ)1-•, Srad = 1/2), and a central Ni(II) ion (d8; S = 1) which are antiferromagnetically coupled yielding the observed St = 0 ground state. This result has been confirmed by broken symmetry DFT calculations of 1. In contrast, the St = 3/2 ground state of 3 is more difficult to understand: the two resonance structures [CoIII(3LISQ)(3LPDI)] ↔ [CoII(3LPDI)(3LIBQ)] might be invoked (for tetrahedral [CoII(3LISQ)2] containing an SCo = 3/2 with two antiferromagnetically coupled π-radical ligands an St = 1/2 is anticipated). Complex 2 is diamagnetic (S = 0) containing a PdII ion (d8, SPd = 0 in an almost square planar ligand field) and two antiferromagnetically coupled ligand radicals (Srad = 1/2). The electrochemistry and spectroelectrochemistry of 1,2, and 3 have been studied, and electron-transfer series comprising the species [M(L)2]z (z = 2+, 1+, 0, 1−, 2−) have been established. All oxidations and reductions are ligand centered.
