Preparation of pyrazine-bridged, polymeric complexes of ruthenium(II)

.mu.-Pyrazine polynuclear mixed-valence species based on trans ruthenium tetraammines

“…In this connection, it is important to note that the mixed-valence [3,2,2] species derived from [(NH3)5Ru(pz)Ru(bpy)2pzRu(NH3)5]7+ does not show significant absorption at lower energies. 13 The difference from [NH3Ru3NH3]7+ is understandable on the basis that the 7rd levels in Ru(bpy)2 are very much stabilized relative to those of the middle ruthenium in NH3Ru3NH3 and thus there is little admixture of [2,3,2] to the ground state in the Ru(bpy)2…”

“…µ 1. It probably corresponds to [3,2,3] for which only a single "intervalence transition" is possible-this statement is made with the qualification that the systems may be well in the direction of being valence delocalized. In the case of pzRu3pz, a unique assignment of the oxidation stages is possible because of the particular symmetry but this is not the case for pzRu4pz, where the molecule has two sets of equivalent sites.…”

Ru(ii) complexes with diazine ligands: electronic modulation of the coordinating group is key to the design of “dual action” photoactivated agents

“…The complexes were prepared under low light conditions by refluxing cis- [Ru(bpy) 2 Cl 2 ] with a 10-fold excess of the desired diazine in ethanol:water (1:1). Complexes 1 , 2 and 4 have been reported previously, 31–32 including the photophysical properties 33 and some photosubstitution reactions 34 for complexes 1 and 2 . NMR spectroscopy and X-ray crystal structure have been reported for 1 , 32 though noteworthy differences were found in the NMR of compound 1 .…”

Synthesis of 2-picolyl functionalized η5-cyclopentadienyl derivatives of rhodium(I) and iridium(I) and preliminary study of their reaction with ruthenium(II) for assembling hetero-bimetallic complexes

“…2-Picolylcyclopentadiene [4], 2-picolylcyclopentadienylthallium(I) (8) [4] [owing to their toxicity, all thallium derivatives must be handled with care], (g 5 -2-picolylcyclopentadienyl)dicarbonylrhodium(I) (5) [4], di-l-chlorobis-(g 4 -cycloocta-1,5-diene)dirhodium(I) [21], di-l-chlorobis(g 4 -cycloocta-1,5-diene)diiridium(I) [22], chlorodicarbonyl(pyridine)iridium(I) [10], (g 5 -cyclopentadienyl)(g 4 -cycloocta-1,5-diene)rhodium(I) (9) [6], (g 5 -cyclopentadienyl)(g 4 -cycloocta-1,5-diene)iridium(I) (10) [7], (g 5 -cyclopentadienyl)dicarbonylrhodium(I) (11) [9], and (g 5 -cyclopentadienyl)dicarbonyliridium(I) (12) [10], potassium azide [23], bis(2,2 0 -bipyridine)chloronitrosylruthenium(II)-bis-(hexafluorophosphate) (14) [18] were prepared as reported. n-Butyllithium 1.6 M in hexane (Aldrich) was used as received.…”