When [TeFe3(CO)9]2- was treated with 1 equiv of propargyl bromide in MeCN, the novel acyl complex [Et 4N][(μ3-Te)Fe3(CO) 9(μ3-η1: η1η3C(O)C(H)CCH2)] ([Et 4N]) was obtained. Cluster 1 can be viewed to consist of a TeFe3 core which is linked by the novel allylcarbonyl ligand C(O)CHCCH2 in a μ3-η1:η1: η3 fashion. Further oxidation of cluster 1 occurs via organo ligand loss and bond rearrangement to give the oxidation product Te 2Fe3(CO)9. In addition, when cluster 1 was methylated with CF3SO3Me, the Fischer-type carbene complex (μ3-Te)Fe3(CO)9(μ3- η1:η1:η3-C(OMe)C(H)CCH 2) (2) was afforded. When the ratio of reactants and reaction solvent was varied, the detailed reaction of [TeFe3(CO)9] 2- with propargyl bromide could be further investigated. When [TeFe3(CO)9]2- was treated with excess propargyl bromide in MeCN, the two new butterfly clusters Te2Fe 2(CO)6(CH=C=CH2)2 (3) and Te 2Fe2(CO)6(CH2C≡CH)(CH=C= CH2) (4) were obtained along with cluster 1. While cluster 3 displays a Te2Fe2 metal core with two allenyl ligands attached to the tellurium atoms in anti positions, cluster 4 consists of a Te 2Fe2 core with each tellurium atom coordinated to one allenyl or one propargyl ligand in an anti position. Further investigation of [TeFe3(CO)9]2- with propargyl bromide in a molar ratio of 1:2 or 1:4 in CH2Cl2 showed that the oxidation product (μ3-Te)Fe3(CO) 9(μ3-η1:η2: 1-C(Me)=CH) (5) was afforded, in addition to the formation of 1, 3, and 4. Cluster 5 can be viewed to be composed of a TeFe3 core coordinated with the propyne ligand C(Me)≡CH, which acts as a 4e donor. This paper describes the detailed reactions of [TeFe3(CO) 9]2- with the bifunctional propargyl bromide in terms of the reaction solvents, the ratio of the reactants, and the chalcogen effect, and the reactivities and structural features of the resultant clusters with the novel organo moieties are systematically compared and discussed.
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