Experimental Evidence for the Noninnocence of o-Aminothiophenolates: Coordination Chemistry of o-Iminothionebenzosemiquinonate(1-) π-Radicals with Ni(II), Pd(II), Pt(II)

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Abstract
The ligand 2-mercapto-3,5-di-tert-butylaniline, H[LAP], an o-aminothiophenol, reacts with metal(II) salts of Ni and Pd in CH3CN or C2H5OH in the presence of NEt3 under strictly anaerobic conditions with formation of beige to yellow cis-[MII(LAP)2] (M = Ni (1), Pd (2)) where (LAP)1- represents the o-aminothiophenolate(1-) form. The crystal structure of cis-[PdII(LAP)2][HN(C2H5)3][CH3CO2] has been determined by X-ray crystallography. In the presence of air the same reaction produces dark blue solutions from which mixtures of the neutral complexes trans/cis-[MII(LISQ)2] (M = Ni (1a/1b), Pd (2a/2b), and Pt (3a/3b)) have been isolated as dark blue−black solid materials. By using HPLC the mixture of 3a/3b has been separated into pure samples of 3a and 3b, respectively; (LISQ)1- represents the o-iminothionebenzosemiquinonate(1-) π-radical. The structures of 1a·dmf and 3a·CH2Cl2 have also been determined. All compounds are square-planar and diamagnetic. 1H NMR spectroscopy established the cis ⇋ trans equilibrium of 1a/1b, 2a/2b, and 3a/3b in CH2Cl2 solution where the isomerization rate is very fast for the Ni, intermediate for the Pd, and very slow for the Pt species. It is shown that the electronic structures of 1a/1b, 2a/2b, 3a, and 3b are best described as diradicals with a singlet ground state. The spectro- and electrochemistries of all complexes display the usual full electron transfer series where the monocation, the neutral species, the mono- and dianions have been spectroscopically characterized. X-band EPR spectra of the monocations [1a/1b]+ and [3a]+ support the assignment of an oxidation-state distribution as predominantly [MII(LISQ)(LIBQ)]+ where (LIBQ)0 represents the o-iminothionequinone level. In contrast, the EPR spectra of the monoanions [1a/1b]- and [3a]- indicate an [MII(LISQ)(LAP−H)]- distribution but with a significant contribution of the [MI(LISQ)2]- resonance hybrid; (LAP−H)2- represents the o-imidothiophenolato(2-) oxidation level. Analysis of the geometric features of 120 published structures of complexes containing ligands of the o-aminothiophenolate type show that high precision X-ray crystallography allows to discern the differing protonation and oxidation levels of these ligands. o-Aminothiophenolates are unequivocally shown to be noninnocent ligands; the (LISQ)1- radical form is quite prevalent in coordination compounds and the electronic structure of a number of published complexes must be reconsidered.

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