25411-98-7Relevant articles and documents
Reactions of secondary dithioxamides with [(η6-p-cymene)RuCl(μ-Cl)]2: The role of steric hindrance on amidic nitrogen in determining the reaction products
Lanza, Santo,Bruno, Giuseppe,Nicolo, Francesco,Rotondo, Archimede,Tresoldi, Giuseppe
, p. 65 - 72 (2007/10/03)
The reactions of secondary dithioxamides H2R2DTO 1-11 [R = methyl 1, ethyl 2, n-propyl 3, n-butyl 4, isoamyl 5, benzyl 6, p-tolyl 7, (R)-1-phenylethyl 8, (R,S)-1-phenylethyl 9, isopropyl 10, cyclohexyl 11] with the chloride-bridge dimer [(η6p-cymene)RuCl(μ-Cl)]2 complex readily afforded either bimetallic ruthenium complexes of formula [(η6-p-cymene)RuCl2](μ-R2DTO) (R = methyl 12a, R = ethyl, 12b, R = n-propyl 12c; R = n-butyl 12d; R = isoamyl 12e; R = benzyl 12f; R = p-tolyl 12g) or mononuclear "piano stool" geometry ion pairs {(η6-p-cymene)RuCl (H2R2DTO)+,(Cl-) κ-S,S′ Ru} [R = (R)-1-phenylethyl, 13a; R = (R,S)-1-phenylethyl, 13b; R = isopropyl, 13c; R = cyclohexyl, 13d]. The driving force of the reactions was the bulkiness of the R groups attached to dithioxamides, leading respectively from primary and aromatic N-bonded carbons to neutral bimetallic species 12a-g, or from secondary N-bonded carbons to monometallic 13a-d species. These latter compounds could be easily dehydrohalogenated to give neutral "piano stool" complexes [(η6-p-cymene)RuCl(HR2DTO) κ-S,S′ Ru] [R = (R)-1-phenylethyl 14a; R = (R,S)-1-phenylethyl 14b; R = isopropyl 14c; R = cyclohexyl 14d]. All complexes were characterised in solution by 1H and 13C{1H} NMR spectroscopy. Complex 12f was also characterised by mass spectrometry, and 12g by solid state X-ray crystallography.
