Abstract
Treatment of the ruthenium acetylide complexes [M]C⋮CPh (1a, [M] = [Ru] = Cp(Ph2PCH2CH2PPh2)Ru; 1b, [M] = [Ru‘] = Cp(PPh3)[P(OMe)3]Ru) with 1.1 equiv of EtO2CNCS results in [2 + 2] cycloadditions yielding the four-membered-ring 2-iminothiete products 2a,b, respectively. Isomerization of complex 2a results in formation of 3a containing the six-membered-ring oxazinethione ligand. Alkylation of complex 3a by CH2Cl2 takes place at the thione sulfur to give 4a, which loses ethyl chloride, yielding the new six-membered-ring [1,3]-oxazin-2-one complex 5a. Further alkylation of 3a by the chloromethyl group of 5a affords the dinuclear complex 6a with two oxazin-2-one ligands bridged by a methylene group. Structures of 2b, 3a, 5a and 6a have been determined by single-crystal X-ray diffraction analysis.
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