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Syntheses and Single-Crystal X-ray Diffraction Studies of Acyclic and Macrocyclic Aza Dithiolate (NS2) Complexes of (Arene)ruthenium(II). Thiolate Alkylation, Base-Promoted Hydroalkylation, and Protonation Reactions

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journal contribution
posted on 20.12.2004, 00:00 by Richard Y. C. Shin, Geok Kheng Tan, Lip Lin Koh, Lai Yoong Goh
The complex [(HMB)Ru{η3-HN(CH2CH2S)2}] (2), synthesized from the reaction of [(HMB)RuCl2]2 (HMB = η6-C6Me6) with HN(CH2CH2S-)2, undergoes S-alkylation reactions with (i) Br(CH2)nBr (n = 2−4), giving [(HMB)Ru{η3-S(CH2)2NH(CH2)2S(CH2)n}](PF6)2 (n = 2 (3), 3 (4), 4 (5)), which contain macrocyclic zNS2 (z = 9−11) ligands, (ii) CH3I, giving [(HMB)Ru{η3-NH(CH2CH2SMe)2}](I·PF6) (6), and (iii) bromoalkenes CH2CH(CH2)nBr (n = 1, 2), yielding the S-alkenyl derivatives [(HMB)Ru{η3-S(CH2)2NH(CH2)2SCH2CHCH2}]PF6 (7), [(HMB)Ru{η3-NH((CH2)2SCH2CHCH2)2}](Br·PF6) (8), and [(HMB)Ru{η3-S(CH2)2NH(CH2)2S(CH2)2CHCH2}]PF6 (9). Deprotonation of 3 and 7 results in the formation of arene-tethered complexes, viz. [Ru{η63-C6Me5(CH2)3S(CH2)2NH(CH2)2S}]PF6 (11), from 3 via [(HMB)Ru{η3-S(CH2)2NH(CH2)2SCHCH2)}]PF6 (10), which can be reverted to 3 with acid treatment, and [Ru{η63-C6Me5CH2CH(Me)CH2S(CH2)2NH(CH2)2S}]PF6 (12) from 7. The X-ray crystal structures of 2, 3, and 512 are reported.

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