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https://doi.org/10.1021/om049445c
Title: | Syntheses and single-crystal X-ray diffraction studies of acyclic and macrocyclic aza dithiolate (NS 2) complexes of (arene)ruthenium(II). Thiolate alkylation, base-promoted hydroalkylation, and protonation reactions | Authors: | Shin, R.Y.C. Tan, G.K. Koh, L.L. Goh, L.Y. |
Issue Date: | 20-Dec-2004 | Citation: | Shin, R.Y.C., Tan, G.K., Koh, L.L., Goh, L.Y. (2004-12-20). Syntheses and single-crystal X-ray diffraction studies of acyclic and macrocyclic aza dithiolate (NS 2) complexes of (arene)ruthenium(II). Thiolate alkylation, base-promoted hydroalkylation, and protonation reactions. Organometallics 23 (26) : 6293-6298. ScholarBank@NUS Repository. https://doi.org/10.1021/om049445c | Abstract: | The complex [(HMB)Ru{η 3-HN(CH 2CH 2S) 2}] (2), synthesized from the reaction of [(HM-B)RuCl 2] 2 (HMB = η 6-C 6Me 6) with HN(CH 2CH 2S -) 2, undergoes S-alkylation reactions with (i) Br(CH 2) nBr (n = 2-4), giving [(HMB)Ru{η 3- S(CH 2) 2NH(CH 2) 2S(CH 2) n}](PF 6) 2 (n = 2 (3), 3 (4), 4 (5)), which contain macrocyclic zNS 2 (z = 9-11) ligands, (ii) CH 3I, giving [(HMB)-Ru{η 3-NH(CH 2CH 2SMe) 2}](I·PF 6) (6), and (iii) bromoalkenes CH 2=CH(CH 2) nBr (n = 1, 2), yielding the S-alkenyl derivatives [(HMB)Ru{η 3-S(CH 2) 2NH(CH 2) 2SCH 2CH=CH 2}]PF 6 (7), [(HMB)Ru{η 3-NH((CH 2) 2SCH 2CH=CH 2) 2}] (Br·PF 6) (8), and [(HMB)Ru{η 3-S(CH 2) 2NH(CH 2) 2S-(CH 2) 2CH=CH 2}]PF 6 (9). Deprotonation of 3 and 7 results in the formation of arene-tethered complexes, viz. [Ru{η 6:η 3-C 6Me 5(CH 2) 3S(CH 2) 2NH(CH 2) 2S}] PF 6 (11), from 3 via [(HMB)Ru-{η 3-S(CH 2) 2NH(CH 2) 2SCH=CH 2)}]PF 6 (10), which can be reverted to 3 with acid treatment, and [Ru{η 6:η 3-C 6Me 5CH 2CH(Me)CH 2S(CH 2) 2NH(CH 2) 2S}]PF 6 (12) from 7. The X-ray crystal structures of 2, 3, and 5-12 are reported. | Source Title: | Organometallics | URI: | http://scholarbank.nus.edu.sg/handle/10635/95012 | ISSN: | 02767333 | DOI: | 10.1021/om049445c |
Appears in Collections: | Staff Publications |
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