摘要：

Solvolysis of [RhMe(CF 3 SO 3 ) 2 (Me 3 [9]aneN 3 )] ( 1 ) (Me 3 [9]aneN 3 = 1, 4, 7-trimethyl-1, 4, 7-triazacyclononane) in CH 3 CN, DMSO or pyrazole (L) leads to substitution of both trifluoromethylsulfonate ligands and formation of the cationic complexes [RhMeL 2 (Me 3 [9]aneN 3 )](CF 3 SO 3 ) 2 3—5 . In contrast, treatment of [RuCl 3 (Me 3 [9]aneN 3 )] ( 2 ) with Ag(CF 3 SO 3 ) in a 1:3 ratio for 2h in CH 3 CN leads to formation of the tetranuclear complex [{RuCl 3 (Me 3 [9]aneN 3 )} 2 Ag 2 (CF 3 SO 3 )(CH 3 CN)](CF 3 SO 3 ) · CH 3 CN ( 6 ) with a novel [(RuCl 3 ) 2 Ag 2 ] core. More forcing conditions enable the substitution of respectively one or two chloride ligands by CH 3 CN (reflux 18h) or DMF (85°C, 1h) to afford [RuCl 2 (CH 3 CN)(Me 3 [9]aneN 3 )](CF 3 SO 3 ) ( 7 ) and [RuCl(DMF) 2 (Me 3 [9]aneN 3 )](CF 3 SO 3 ) 2 ( 8 ). The heteroleptic sandwich complex [Ru([9]aneS 3 )(Me 3 [9]aneN 3 )](CF 3 SO 3 ) 2 ( 9 ) can be prepared by reduction of 2 with Zn powder in acetone in the presence of 3 equiv. of Ag(CF 3 SO 3 ), followed by addition of [9]aneS 3 (1, 4, 7-trithiacyclononane). The redox potential E°(Ru 3+ /Ru 2+ ) of +1.87 V vs NHE for 9 is only —0.12 V lower than that of the homoleptic complex [Ru([9]aneS 3 ) 2 ] 2+ . Crystal structures are reported for 3 — 9 .

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