Alkynes, reactions with carbonyl clusters

This article is concerned with one specific aspect of cluster organometallic chemistry, and describes the synthesis, characterization, structure, and reactivity of transition metal clusters containing alkyne, or alkyne-derived ligands. Alkynes display a diverse reactivity in their reactions with carbonyl clusters, and exhibit a wider range of coordination modes than any other simple, unsaturated molecule. It is this compelling diversity that has prompted the authors to undertake this review. 

Reaction of Fe3(CO)12 with 3-pentyn-l-ol gives the hydrido cluster 4, formed by coupling of an allenylidene unit with a coordinated carbonyl ligand and methoxy group. In contrast, reaction with the isomeric alkyne 2-methyl-3-butyn-2-ol affords a binuclear iron complex.18 Treatment of Fe3(p3-S)2(CO)9 with Me3NO affords the vinylferrocene complex 5, whereas the similar reaction with Fe3(p3-Te)2(CO)9 gives no cluster products.19... 

Carbyne ligands may bridge two (p) or three (p3) metal centres, providing a total of 3VE to the overall electron count. Earlier synthetic routes to such complexes involved the reactions of carbonyl metallates with 1,1,1-trihaloalkanes, or the cleavage of alkyne ligands coordinated to clusters (Figure 5.46). 

Although the reactions between alkynes or alkenes and metal clusters are the main source of alkyne-substituted complexes, there are other reagents which can produce similar products. Two such reagents are tetraphenylcyclopentadienone, which in the reaction with Ru3(CO)i2 produces Ru3(CO)10(PhCCPh) (167), and dimethyl-vinylarsine, which has been made to react with several carbonyl clusters [Eq. (8)] (168, 169). In the reaction of M3(CO)12 (M = Ru, Os) with a number of tertiary phosphines and aromatic alcohols, an oxidative addition takes place and benzyne-triosmium compounds are obtained (170-176). The fact that Os3(CO)uPEt3 can be converted into an alkyne compound (177) suggests that the conversion goes through substituted intermediates. Carbene derivatives of clusters have also... 

Alkynes containing methylene (—CHi—) functionalities a to the triple bond readily undergo thermal C-H activation under conditions necessary to initiate reaction with group VIII metal carbonyls (54). The allenyl clusters obtained isomerize thermally via a 1,2-hydrogen atom shift to afford the thermodynamically more favorable 1,3-dimetalloallyl clusters (Table 1) (49,55). A similar chemistry has been recognized for osmium clusters, albeit under more severe conditions. 

The jt-related II is obtained in 42% when Fe3(CO)i2 is refluxed in methylcyclohexane with di-t-butylacetylene The reactions of alkynes with tri- and tetrametallic carbonyl clusters of Fe, Ru and Os produce few ( -alkyne) products, but their formation follows a more complex pathway than the simple CO displacement, e.g., the compound Ru4(CO)i2(/- f"-RC2R) ... 

In contrast, when thiophenes react with triosmium carbonyl clusters it is C-H bond activation that occurs in preference to C-S bond cleavage. The direct reaction of [Os3(CO)i2], or the -acetonitrile complex [Os3(CO)io(NCMe)2], with thio-phene results in the oxidative addition of a C-H bond to give the exo- and endo isomers of the n, -thienyl hydrido cluster [Os3(//-H)(/z-C4H3S)(CO)io] (21a, 22a) (Scheme 7). These isomers are in rapid equilibrium at room temperature. The complex [Os3(/i-H)2(/X3-C4H2S)(CO)9] (23a) also results from his reaction, presumably by additional thermal C-H bond activation and decarbonylation of the thienyl complex. This cluster contains a triply bridging cyclic alkyne ligand related to /i3-benzyne. " ... 

Examples of 0x0 clusters obtained from metal alkoxides have been reported and the analogy between [W4Cl(0)(0Pr )9] and [W4(0)(OPr )io] and tetrahedral carbonyl clusters has been discussed. Trirhenium neopentoxide clusters give interesting reactions with ethylene and alkynes. ... 

E3.25 Reactions of ruthenium carbonyl clusters with alkynes... 

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