An Approach to Carbide-Centered Cluster Complexes

Abstract

We report the first examples of the carbide ligand in (Cy3P)2Cl2RuC (RuC) developing into a μ3 ligand toward metal centers. Conventionally, sterics exclude this coordination mode, but Fe2(CO)9 and Co2(CO)8 expel bridging CO ligands upon reaction with RuC to form trimetallic (Cy3P)2Cl2RuCFe2(CO)8 (RuCFe 2 ) and (Cy3P)2Cl2RuCCo2(CO)7 (RuCCo 2 ) complexes. Thus, the proximity offered by metal–metal associations in bimetallic carbonyl complexes allows the formation of trinuclear carbide complexes as verified by NMR, Mössbauer, and X-ray spectroscopic techniques.

Parent Cyclopentadienyl Ruthenium(II) Chloride Synthon: Derivatization to CpRu Amido, Imido, and Oxo Complexes

“…The optimized structure of 12 is shown in Figure . The μ 3 -carbido ligand in 12 adopts a trigonal planar geometry, which perfectly resembles that in 12* and has been rarely seen. , The Ru–carbido distances in 12 (1.923 and 1.926 Å) are comparable to those in 12* (1.926 and 1.929 Å), indicating that the difference between the Cp and Cp* ligands merely affects the nature of the Ru–carbido bonding in these complexes. The Cu–C distance in 12 (1.855 Å) is, on the other hand, slightly shorter than that in 12* (1.876 Å), probably due to the decreased steric bulk of the diruthenocarbene ligand {(CpRu) 2 (μ-N t Bu)­(μ-C)} ( 13 ) than its Cp* analogue 13* .…”

From Ylides to Doubly Yldiide-Bridged Iron(II) High Spin Dimers via Self-Protolysis

“…Known strategies are, for example, the conversion or substitution of CO ligands in polyironcarbonyl clusters into μ 3 -, μ 5 -, or μ 6 -C-ligands to yield, e.g., clusters of type B (Chart 1). 8 Unfortunately, these clusters contain strong-field CO ligands and are low-spin complexes, in contrast to the sulfide ligated high spin iron sites in FeMoco.…”

Isonitrile μ2-carbido complexes

“…It should also be noted that the bonding of Class C carbido complexes has been interpreted in terms of the [Ru(C)Cl 2 (PCy 3 ) 2 ] educt serving as a synergic σ-donor/π-acceptor 3,35 to a range of extraneous metal–ligand fragments. 4 c ,36 Accordingly, there is some use in comparing the distinction between Class B and C carbidos to that between isoelectronic CN − vs. CO ligands.…”