Tetrakis(tert-butyl isocyanide-2κC)dichloro-1κCl,3κCl-di-μ-cyano-1κN:2κC;2κC:3κN-bis[1,3(η⁴)-cycloocta-1,5-diene]dirhodium(I)ruthenium(II)

Abstract

The title compound, [Rh2Ru(CN)2Cl2(C8H12)2(C5H9N)4], was obtained from the reaction of the chloro­(1,5‐cyclo­octa­diene)rhodium(I) dimer with trans‐dicyano­tetra­(tert‐butyl isocyanide)ruthenium(II) by cleavage of the chloro bridges in the dimeric rhodium starting complex. The mol­ecular structure shows the Ru atom in a nearly ideal octa­hedral coordination geometry, whereas the Rh atoms are situated in square‐planar ligand environments. The central ruthenium ion is located on a crystallographic twofold axis. The crystal structure is realized by infinite chains of the trinuclear complex units which are connected by C—H⋯Cl inter­actions. These chains are further linked by another C—H⋯Cl inter­action to produce the observed three‐dimensional structure.

Heterometallic cyanide-bridged complexes containing RhIRuIIRhI triad: NMR data on exchange reactions and ligand effect transmission

“…Thus the NCRuCN fragment in I is far from the perfectly linear configuration observed [14] in the solvated ruthenium complex, trans-[RuPy 4 (CN) 2 ]Á2MeCN. The most notable deflections show CNRh angles, 171.3(2)°and 169.3(2)°, which values fall in-between those found for (Cod)ClRhNC and (CO) 2 ClRhNC fragments in the structures studied earlier [17,23]. Accumulation of these unidirectional deflections, together with those of RhCO ($177.5(2)°for trans-N carbonyl groups) and CRhN ($175.44(8)°) angles, makes the (OC)Rh(NC)Ru(CN)Rh(CO) chain markedly bow-shaped, what, to some extent, can be seen also in the structure [(Cod)ClRh(NC)-Ru(Bu t NC) 4 (CN)RhCl(Cod)] [17].…”

“…The most notable deflections show CNRh angles, 171.3(2)°and 169.3(2)°, which values fall in-between those found for (Cod)ClRhNC and (CO) 2 ClRhNC fragments in the structures studied earlier [17,23]. Accumulation of these unidirectional deflections, together with those of RhCO ($177.5(2)°for trans-N carbonyl groups) and CRhN ($175.44(8)°) angles, makes the (OC)Rh(NC)Ru(CN)Rh(CO) chain markedly bow-shaped, what, to some extent, can be seen also in the structure [(Cod)ClRh(NC)-Ru(Bu t NC) 4 (CN)RhCl(Cod)] [17]. Contrary to anti-(Cl, Cl) configuration in the last structure, chlorido ligands in I are nearly syn- [25]), molecules I form an infinite ladder-shaped sequence along the c-axis of the crystal (Fig.…”

“…The preliminary data on these complexes including their spectral (IR and 13 C NMR) parameters and X-ray data for I were briefly reported in our presentations [16]. The first example of the family, [(Cod)ClRh(NC)Ru(Bu t NC) 4 (CN)RhCl(Cod)], has been structurally characterized recently [17]. [19,20] for the doublet at 183.4 ppm, we assign it to the carbonyl carbon trans to cyanide nitrogen.…”