Higher nuclearity Fe,Ru mixed-metal dicarbide cluster compounds derived from ethynediyldiiron complex (eta(5)-C5Me5)(CO)(2)Fe-C C-Fe(eta(5)-C5Me5)(CO)(2)

Reaction of the ethynyliron complexes FP-C equivalent toC-H [FP = Fp (1), F p* (1*); Fp = (eta (5)-C5H5)-)Fe(CO)(2); Fp* = (eta (5)-C5Me5)Fe(CO)(2)] wi th Ru-3(CO)(12) in refluxing benzene affords triruthenium mu-eta (1)(Ru1):e ta (2)(Ru2):eta (2)(Ru3)-acetylide cluster type compounds Ru-3(CO)(9)[mu (3 )-eta (1):eta (2):eta (2)-C equivalent toC-FP] [FP = Fp (3), Fp* (3*)] in a manner similar to the reaction of l-alkynes. In contrast to the clean reac tion of 1 and 1*, reaction of the ethynediyldiiron complex, Fp*-C equivalen t toC-Fp*(2*), gives a complicated mixture of products, from which Cp*2Fe2R u2(mu (4)-C-2)(CO)(10) (5*) and Cp*(2)-Fe2Ru6(mu (6)-C-2)(CO)(17) (6*) are isolated and characterized as permetalated ethene and permetalated ethane, respectively, by X-ray crystallography. It is revealed that the permetalate d hydrocarbon structures in 5* and 6* are constructed via formal addition o f a dimetallic species to the C-C triple bond in 2*. The octanuclear comple xes 6* and 6 (Cp derivative) are also prepared by thermal dimerization of t he tetranuclear FeRu3(mu -C-2) core in 3* and 3. Higher nuclearity cluster compounds including the heptanuclear dicarbide cluster compound CpFeRu6(mu (5)-C-2)(mu (5)-C2H)(CO)(16) (12) and the heptanuclear bis(dicarbide) clust er compound Cp2Fe2Ru5(mu (5)-C-2)(2)(CO)(17) (15) are obtained not only by thermolysis but also by one-electron oxidation of the deprotonated anionic form of 3 (13).