Zusammenfassung
Reactions of the [Os3H2(CO)(10)] cluster complex (1) with six-membered heterocyclic amines (morpholine, thiomorpholine, piperidine) and halohydrocarbons (CH2Cl2, ClHC=CHCl, CH2=CCl2) at similar to 25 degrees C have been studied. Two main types of products are formed in all studied reactions. One product is carbene cluster [Os-3(mu-H)(mu-Cl){eta(1)-C(CH3)N(CH2CH2)(2)X}(CO)(9)] (X=O, S, CH2) (3, 3 ...
Zusammenfassung
Reactions of the [Os3H2(CO)(10)] cluster complex (1) with six-membered heterocyclic amines (morpholine, thiomorpholine, piperidine) and halohydrocarbons (CH2Cl2, ClHC=CHCl, CH2=CCl2) at similar to 25 degrees C have been studied. Two main types of products are formed in all studied reactions. One product is carbene cluster [Os-3(mu-H)(mu-Cl){eta(1)-C(CH3)N(CH2CH2)(2)X}(CO)(9)] (X=O, S, CH2) (3, 3 a and 3 b). Second product is cluster containing enamine ligand [Os-3(mu-H){mu-CH=CHN(C2CH2)(2)X)}(2)(CO)(10)] (X=O, S, CH2) (2, 2 a and 2 b). The carbene ligand is assembled on a cluster, from three organic molecules, thus representing the first example of carbene ligands formed in this way. Clusters with carbene ligand exist as two stable isomers (rotamers hindered towards the Os-C bond), as confirmed by NMR studies and conformational analysis. We have found that in reactions of cluster 1 with acyclic amines containing an oxygen atom in gamma-position (likely morpholine in CH2Cl2), only complexes with bridging enamine ligands are formed. Compounds 2 a, 2 b, 3 and 3 b are characterized by single-crystal X-ray diffraction.
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