Abstract
The reactions of the hydrido–triruthenium cluster complex [Ru~3~(μ‐H)(μ~3~‐κ^2^‐HNNMe~2~)(CO)~9~] (1; H~2~NNMe~2~=1,1‐dimethylhydrazine) with alkynes that have α‐hydrogen atoms give trinuclear derivatives containing edge‐bridging allyl or face‐capping alkenyl ligands. Under mild conditions (THF, 70 °C) the isolated products are as follows: [Ru~3~(μ~3~‐κ^2^‐HNNMe~2~)(μ‐κ^3^‐1‐syn‐Me‐3‐anti‐EtC~3~H~3~)(μ‐CO)~2~(CO)~6~] (2) and [Ru~3~(μ~3~‐κ^2^‐HNNMe~2~)(μ‐κ^3^‐1‐syn‐Me‐3‐syn‐EtC~3~H~3~)(μ‐CO)~2~(CO)~6~] (3) from 3‐hexyne; [Ru~3~(μ~3~‐κ^2^‐HNNMe~2~)(μ‐κ^3^‐3‐anti‐PhC~3~H~4~)(μ‐CO)~2~(CO)~6~] (4), [Ru~3~(μ~3~‐κ^2^‐HNNMe~2~)(μ‐κ^2^‐MeCCHPh)(μ‐CO)~2~(CO)~6~] (5) and [Ru~3~(μ~3~‐κ^2^‐HNNMe~2~)(μ~3~‐κ^2^‐PhCCHMe)(μ‐CO)~2~(CO)~6~] (6) from 1‐phenyl‐1‐propyne; [Ru~3~(μ~3~‐κ^2^‐HNNMe~2~)(μ‐κ^2^‐3‐anti‐PrC~3~H~4~)(μ‐CO)~2~(CO)~6~] (7), [Ru~3~(μ~3~‐κ^2^‐HNNMe~2~)(μ~3~‐κ^2^‐BuCCH~2~)(μ‐CO)~2~(CO)~6~] (8), and [Ru~3~(μ~3~‐κ^2^‐HNNMe~2~)(μ~3~‐κ^2^‐HCCHBu)(μ‐CO)~2~(CO)~6~] (9) from 1‐hexyne; [Ru~3~(μ~3~‐κ^2^‐HNNMe~2~)(μ~3~‐κ^2^‐HOH~2~CCCH~2~)(μ‐CO)~2~(CO)~6~] (10) from propargyl alcohol; and [Ru~3~(μ~3~‐κ^2^‐HNNMe~2~)(μ~3~‐κ^2^‐MeOCH~2~CCH~2~)(μ‐CO)~2~(CO)~6~] (11) from 3‐methoxy‐1‐propyne. The regioselectivity of these reactions depends upon the nature of the alkyne reagent, which affects considerably the kinetic barriers of important reaction steps and the stability of the final products. It has been established that the face‐capped alkenyl derivatives are not precursors to the allyl products, which are formed via edge‐bridged alkenyl intermediates. At higher temperature (toluene, 110 °C), the complexes that have allyl ligands with an anti substituent are isomerized into allyl derivatives with that substituent in the syn position, for example, 4 into [Ru~3~(μ~3~‐κ^2^‐HNNMe~2~)(μ‐κ^3^‐3‐syn‐PhC~3~H~4~)(μ‐CO)~2~(CO)~6~] (14). The diene complex [Ru~3~(μ‐H)(μ~3~‐κ^2^‐HNNMe~2~)(μ‐κ^4^‐trans‐EtC~4~H~5~)(CO)~7~] (13) has been obtained from the thermolysis of compounds 2 and 7 at 110 °C (3 and [Ru~3~(μ~3~‐κ^2^‐HNNMe~2~)(μ‐κ^2^‐3‐syn‐PrC~3~H~4~)(μ‐CO)~2~(CO)~6~] (12) are also formed in these reactions). A DFT theoretical study has allowed a comparison of the thermodynamic stabilities of isomeric compounds and has helped rationalize the experimental results. Mechanistic proposals for the synthesis of the allyl complexes and their isomerization processes are also provided.