µ₃-Oxotrimetal acetato-complexes of chromium, manganese, iron, cobalt, rhodium, and iridium

Spectroelectrochemical Study of some μ3-Oxo-μ-acetato Trinuclear Rhodium(III) and Iridium(III) Complexes

“…Crystal structures of the aqua complexes have been reported [21]. We have pre viously reported the reversible nature of the oneelectron oxidation process of [Rh3 (/<3 -0)(/^-CH3 C 0 0 ) 6 (p y)3]+ in acetonitrile [7], The one-electron oxidation process of [Ir3 (//3 -0)(//-CH3 C 0 0 ) 6 (p y )3]+ was reported to be irreversible in acetone [18].…”

“…A ll the trirhodium(III) complexes were pre pared by applying the reported methods for [Rh3 (a 3 -0)(/^-CH3 C 0 0 ) 6 (p y )3]+ and its deriva tives [18], An aqueous solution (15 ml) containing 0.5 g of RhCl3 -3H 20 was mixed with an acetic acid solu tion (15 ml) of 0.5 g silver acetate. The mixture was refluxed for 6 h. A fter filtration to remove AgCl, the filtrate was evaporated to dryness.…”

“…Furthermore, the complexes with different oxidation states, such as Ru3 (II,III,III) [15] and Ru3 (III,III,IV ) [24], have been isolated and char acterized structurally. Also, triiridium complexes, [Ir3 (a 3 -0 )(a -C H 3 C 0 0 ) 6 ( L ) 3]" + have been iso lated both in Ir3 (III,III,III) (n = 1; L = py, H 2 0, ß -picoline (/5-pic)) and Ir3 (III,III,IV ) {n = 2; L = H 2 0, P (C 6 H 5) 3, py) states [18]. Recently, pyridine complexes in both oxidation states have been structurally characterized [24], In contrast, the tri- have been isolated only in Rh3 (III,III, III) states [18,26].…”

“…Also, triiridium complexes, [Ir3 (a 3 -0 )(a -C H 3 C 0 0 ) 6 ( L ) 3]" + have been iso lated both in Ir3 (III,III,III) (n = 1; L = py, H 2 0, ß -picoline (/5-pic)) and Ir3 (III,III,IV ) {n = 2; L = H 2 0, P (C 6 H 5) 3, py) states [18]. Recently, pyridine complexes in both oxidation states have been structurally characterized [24], In contrast, the tri- have been isolated only in Rh3 (III,III, III) states [18,26]. Crystal structures of the aqua complexes have been reported [21].…”

“…1 have been proposed for the trinuclear ruthenium complexes [3,15,16], In the study of mixed ruthenium-rhodium complexes, it was suggested that a similar molecular orbital scheme should be appli cable to trirhodium and mixed ruthenium-rhodium complexes [7]. Electronic states o f the oxocentered triiridium (III) complexes [17,18] should also be considered in terms of the djr-pjr molec ular orbital scheme. Thus the oxo-centered tri metal complexes of heavy transition elements could be significantly different from those of first row transition elements with respect to the extent of metal-oxygen-metal interactions.…”