A variety of hexaruthenium carbonyl complexes containing zwitterionic alkenylammonium ligands have been synthesized and characterized by the coupling of simple alkynes to NMe3 generated in reactions involving Me3NO. The reaction of Ru6C(CO)17, 1 with C2H2 and Me3NO yielded the following new zwitterionic compounds: Ru6C(CO)15(µ-η2-C2H2NMe3), 2, and Ru6C(CO)14(µ3-η4-C4H4NMe3), 3. Compound 2 contains an edge-bridging η2-C2H2NMe3 ligand. Compound 3 contains a bridging η4-C4H4NMe3 ligand formed by the coupling of two C2H2 groups and a molecule of NMe3. Addition of CO to 2 yielded the compound Ru6C(CO)16(η1-C2H2NMe3), 4, which contains a terminally coordinated η1-C2H2NMe3 ligand. Compounds 2 and 3 eliminated their NMe3 group when heated to form the compounds Ru6C(CO)15(µ3-C2H2), 5 and Ru6C(CO)14(µ3-η4-C4H4), 6 respectively, see Scheme 1. Compound 6 contains a 1,4-dimetallated-butadiendiyl ligand coordinated to a triangular group of three ruthenium atoms. The reaction of 1 with HC2(CO2Me) and Me3NO yielded Ru6C(CO)16[η1-C(CO2Me)C(H)NMe3], 7 which contains a terminally coordinated η1- C(CO2Me)C(H)NMe3 ligand. Compound 7 was converted to the alkyne complex Ru6C(CO)15(µ3-HC2CO2Me), 8 when heated by elimination of the CO and the NMe3 groupings (Scheme 2).

Zwitterionic-alkenylammonium ligands in hexaruthenium carbido carbonyl complexes: Synthesis and transformations

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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