Acetylide cluster

The reactions of the butadiynediyldimetal(Fe, Ru) complexes with Fe2(CO)ci at room temperature afforded mixtures of products, from which three types of products, viz. the ps-acetylide cluster compound 4, the pj-ti -propargylidene-ketene compound 5 and zwitterionic cluster compound 6, were isolated. While the reaction with an excess amount of Co2(CO)g results in addition to the sterically congested Fp -C=C part [6]. The distributions of the products were dependent on the metal fragments situated at the other end of the conjugated carbon rod. The cluster compounds so obtained were characterized by spectroscopic and... 

Gold(I) ketenide was prepared from [AuCl(2,6-Me2C5H3N)] (67), and this unusual compound reacted with phenylacetylene in the presence of phenylamine to give an acetylide cluster [Eq. (23)]. 

The crystal structure of [PPN][Fe(C0)4 CH(Me)C02Et)], formed by insertion of ethyl acrylate into [HFe(CO)4] , has been published. Reaction of [Fe(CO)4]2- with the acetylide cluster... 

Ethynediyl (fi-Cz) and butadiynediyl (/i-C4) diiron complexes of the formulas, Fp -(C=G) -Fp (n=l 30, 2 31 Fp = Fe(GO)2( 7 -C5Me5)), are converted into the corresponding acetylide cluster complexes 33 and 34, respectively, in a selective manner, when the reactions are carried out in benzene (Scheme 4). The //4-G2 cluster complex 33 derived from 30 shows dynamic behavior via reversible metal-metal bond cleavage and recombination processes. On the other hand, the reaction of 31 in THF gives the /x-ry -propargylidene-ketenyl complex 35 as a byproduct, which is converted into 34 via decarbonylation upon dissolution in benzene. Reaction of the related mononuclear ethynyl complex 32 affords a mixture of the trinuclear acetylide cluster complex 36 and the dimetal-substituted quinone complex 37. 

The chemistry of both Ru-W and Os-W mixed-metal clusters was extensively investigated by Chi et al., and a number of exciting discoveries were made. These include the reversible scission of a coordinated acetylide ligand on the acetylide cluster 168, which can be prepared from the condensation of CpW(CO)3(C2Ph) and Ru3(GO)i2 in refluxing toluene.The carbide clusters 169 and 170 were formed when 168 was heated with Ru3(CO)i2 in heptane. Interestingly, the reaction sequence can be reversed to regenerate the acetylide cluster 168 in the presence of pressurized CO. This kind of reactivity is seldom observed for semi-encapsulated ruthenium carbide systems. 

The reaction of the acetylide cluster [Os3(/z-H)(/x-G=Me)(CO)9] with [Ru3(CO)i2] in refluxing hexane gave [RuOs3(/X4-HC2Me)(GO)i2] with a butterfly metal core. Alkynyl complexes such as [Oss(CO)() fj,-CO)(ii3-ri, 7]. rf-Me3SiG=GG2G=GSiMc3)] also formed mixed-metal clusters 226 when treated with [Ru3(GO)i2] (Table 13). ... 

Polymetallic Complexes Treatment of the acetylide cluster [Cp WRc2(CO)9(C R)] (R = Ph, C(Me)=CH2) with O2 or N2O afforded clusters containing a terminal 0x0 ligand of the type [Cp WRe2(0)(C0)g(CCR)], structurally characterised for R = C(Me)=CH2-Hydrogenation of the cluster afforded three isolable clusters, showing an example of oxo-mediated sequential conversion of acetylide to alkenyl and alkylidene. 

A formal replacement of ( j -C5Me4Et)Fe(CO) moiety of a triiron acetylide cluster compound 73a by an isolobal Co(CO)3 fragment occurs when cluster 73a reacts with [Co2(CO)g] (Scheme 22). " ... 

Reaction of [CpWOs2(CO)8(C = CPh)] with 1.2 equiv. of McsNO in a mixture of dichloromethane-acetonitrile solvent at room temperature followed by in situ reaction with hydride complexes [LW(CO)3H] (L = Cp and Cp ) in refluxing toluene produces the acetylide cluster complexes [CpLW20s2(C0)9(CCPh)(/r-H)]... 

An acetylide cluster, CpWRu2(CO)3(CCPh), was treated with 1 equivalent of Ru3(CO)i2 to give two carbido-alkylidyne cluster complexes, CpWRu4(/i5-C)(CO)i2(ju-CPh) and CpWRu5(/i6-C)(CO)i4(ju-CPh), as shown in Scheme 11 [35]. It is interesting to note that this cleavage is reversible. 

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