Zusammenfassung

The combination of two highly noninnocent ligands with a 3rd-row transition metal produces the title complex ion which was crystd. as Os(Q)2(bpy)(ClO4)·C6H6 (Q = 4,6-di-tert-butyl-o-iminobenzoquinone, bpy = 2,2'-bipyridine) and could be structurally characterized to exhibit a tris-chelate situation at the metal with trans positioned N and cis positioned O donor atoms. The metrical ligand parameters are in agreement with two partially reduced ligands. A 3-spin interaction (Q.bul.-)OsIII(Q.bul.-) can rationalize the obsd. S = 1/2 situation with ligand-centered resulting spin. Ligand-based spin is confirmed by DFT (calcd. spin populations Q: 1.113; Os: -0.113; bpy: 0.001) and is also apparent from the EPR signal (g1 1.981, g2 1.955, g3 1.803, Dg 0.178, 〈g〉 1.915) which is influenced by the high spin-orbit coupling const. of the Os center. The susceptibility measurements reveal antiferromagnetic behavior. A 1-electron oxidn. and two 1-electron redns. could be monitored spectroelectrochem. (UV-visible-NIR) and analyzed by TD-DFT, in comparison with the results from the Ru analog. The anal. reflects the strong orbital mixing between the metal and the two Q-ligand MOs. on SciFinder(R)

Links und Ressourcen

DOI:
10.1039/c2dt30903c
BibTeX-Schlüssel:
Das.2012g
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