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

The complex [(HMB)Ru{η 3 -HN(CH 2 CH 2 S) 2 }] (2), synthesized from the reaction of [(HM-B)RuCl 2 ] 2 (HMB = η 6 -C 6 Me 6 ) with HN(CH 2 CH 2 S-) 2 , undergoes S-alkylation reactions with (i) Br(CH 2 ) n Br (n = 2-4), giving [(HMB)Ru{η 3 -S(CH 2 ) 2 NH(CH 2 ) 2 S(CH 2 ) n }](PF 6 ) 2 (n = 2 (3), 3 (4), 4 (5)), which contain macrocyclic zNS 2 (z = 9-11) ligands, (ii) CH 3 I, giving [(HMB)-Ru{η 3 -NH(CH 2 CH 2 SMe) 2 }](I.PF 6 ) (6), and (iii) bromoalkenes CH 2 =CH(CH 2 ) n Br (n = 1, 2), yielding the S-alkenyl derivatives [(HMB)Ru(η 3 -S(CH 2 ) 2 NH(CH 2 ) 2 SCH 2 CH=CH 2 }]PF6 (7), [(HMB)Ru{η 3 -NH((CH 2 ) 2 SCH 2 CH=CH 2 ) 2 }](Br.PF 6 ) (8), and [(HMB)Ru(η 3 -S(CH 2 ) 2 NH(CH 2 ) 2 S-(CH 2 ) 2 CH=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 6 Me 5 (CH 2 ) 3 S(CH 2 ) 2 NH(CH 2 ) 2 S}]PF 6 (11), from 3 via [(HMB)Ru-{η 3 -S(CH 2 ) 2 NH(CH 2 ) 2 SCH=CH 2 )}]PF 6 (10), which can be reverted to 3 with acid treatment, and [Ru{η 6 :η 3 -C 6 Me 5 CH 2 CH(Me)CH 2 S(CH 2 ) 2 NH(CH 2 ) 2 S}]PF 6 (12) from 7. The X-ray crystal structures of 2, 3, and 5-12 are reported.