The intricate paramagnetic state of Os(Q)2(bpy)+, Q = 4,6-di-tert-butyl-o-iminobenzoquinone
, , , , , , , , , und .
Dalton Transactions 41 (38): 11675--11683 (2012)

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)
  • @b_schwederski
Diese Publikation wurde noch nicht bewertet.

Bewertungsverteilung
Durchschnittliche Benutzerbewertung0,0 von 5.0 auf Grundlage von 0 Rezensionen
    Bitte melden Sie sich an um selbst Rezensionen oder Kommentare zu erstellen.