Synthesis, structure, photophysical and electrochemical behavior of 2-amino-anthracene triosmium clusters

• Published in: Inorganica Chimica Acta 2008-05, Vol.361 (6), p.1624-1633
• Main Authors: Sharmin, Ayesha, Minazzo, Agnese, Salassa, Luca, Rosenberg, Edward, Alexander Ross, J.B., Kabir, Shariff E., Hardcastle, Kenneth I.
• Format: Article
• Language: English
• Subjects: 2-Aminoanthracene; Electrochemistry; Luminescence; Osmium clusters
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2007.03.059

The reaction of 2-aminoanthracene with [Os3(CO)10(CH3CN)2] results in two competitive C–H activations at C(1) and C(3) resulting in two distinct reaction pathways, one of which results in an unusual proton transfer to the amine substituted aromatic ring catalyzed by water. The reactions of 2-amino-anthracene with [Os3(CO)10(CH3CN)2] have been studied and the products structurally characterized by spectroscopic, X-ray diffraction, photophysical and electrochemical techniques. At room temperature in CH2Cl2 two major, isomeric products are obtained [Os3(CO)10(μ-η2-(N-C(1))-NH2C14H8)(μ-H)] (1, 14%) and [Os3(CO)10(μ-η2-(N-C(3))-NHC14H9)(μ-H)] (2, 35%) along with a trace amount of the dihydrido complex [Os3(CO)9(μ-η2-(N-C(3))-NHC14H8)(μ-H)2] (3). In refluxing tetrahydrofuran only complexes 2 and 3 are obtained in 24% and 28%, respectively. A separate experiment shows that complex 1 slowly converts to 2 and that the rearrangement is catalyzed by adventitious water and involves proton transfer to the anthracene ring. Complex 1 is stereochemically non-rigid; exhibiting edge to edge hydride migration while 2 is stereochemically rigid. Complex 3 is also stereochemically non-rigid showing a site exchange process of the magnetically nonequivalent hydrides typical for trinuclear dihydrides. Interestingly, 2 decarbonylates cleanly to the electronically unsaturated 46e− cluster [Os3(CO)9(μ3-η2-(N-C(3))-NHC10H9)(μ-H)] (4, 68%) in refluxing cyclohexane, while photolysis of 2 in CH2Cl2 yields only a small amount of 3 along with considerable decomposition. The mechanism of the conversion of 1 to 2 and the dependence of the product distribution on solvent are discussed. All four compounds are luminescent with compounds 1–3 showing emissions that can be assigned to radiative decay associated with the anthracene ligand. Complexes 1–3 all show irreversible 1e− reductions in the range of −1.85–2.14V while 4 shows a nicely reversible 1e− wave at −1.16V and a quasi-reversible second 1e− wave at −1.62V. Irreversible oxidations are observed in the range from +0.35 to +0.49V. The relationship between the cluster ligand configurations and the observed electrochemical and photochemical behavior is discussed and compared with that of the free ligand.