In this study, Ru complexes [(η-p-cymene)RuX(2-{(2,6-iPr-CH)N=CH}-CHN-6-(O))] (3: X=Cl; 4: X=I) were prepared with N-bound 2-pyridonato ligand by thermal base-free MeX elimination from ionic N,N-chelated Ru complexes [(η-p-cymene)RuX(κ-L)](X) (1: X=Cl; 2: X=I; L={2-[(2,6-iPr-CH)N=CH]-6-(OMe)CHN}). The Ru complex 3 was used as O-donor for Lewis (LA) or Brönsted acids. The reactions of 3 with SnCl, PhSnCl, ZnCl or HCl provided [(η-p-cymene)Ru(SnCl)(2-{(2,6-iPr-CH)N=CH}-CHN-6-(O→SnCl)] (6), [(η-p-cymene)RuCl(2-{(2,6-iPr-CH)N=CH}-CHN-6-(O→SnPhCl)] (7), and [(η-p-cymene)RuCl(2-{(2,6-iPr-CH)N=CH}-CHN-6-(O→)](μ-ZnCl) (8) and [(η-p-cymene)RuCl(2-{(2,6-iPr-CH)N=CH}-CHN-6-(OH)}](Cl) (9). The easy conversion of the 2-pyridonato ligand in 3 to its 2-hydroxypyridine in 9 evoked testing of 3 and 4 as potential catalysts in base-free transfer-hydrogenation of ketones.
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Ruthenium Complexes with N-Bound 2-Pyridonato Ligand as O-Donors: A New Synthetic Approach and the Effect on Reactivity.
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In this study, Ru complexes [(η-p-cymene)RuX(2-{(2,6-iPr-CH)N=CH}-CHN-6-(O))] (3: X=Cl; 4: X=I) were prepared with N-bound 2-pyridonato ligand by thermal base-free MeX elimination from ionic N,N-chelated Ru complexes [(η-p-cymene)RuX(κ-L)](X) (1: X=Cl; 2: X=I; L={2-[(2,6-iPr-CH)N=CH]-6-(OMe)CHN}). The Ru complex 3 was used as O-donor for Lewis (LA) or Brönsted acids. The reactions of 3 with SnCl, PhSnCl, ZnCl or HCl provided [(η-p-cymene)Ru(SnCl)(2-{(2,6-iPr-CH)N=CH}-CHN-6-(O→SnCl)] (6), [(η-p-cymene)RuCl(2-{(2,6-iPr-CH)N=CH}-CHN-6-(O→SnPhCl)] (7), and [(η-p-cymene)RuCl(2-{(2,6-iPr-CH)N=CH}-CHN-6-(O→)](μ-ZnCl) (8) and [(η-p-cymene)RuCl(2-{(2,6-iPr-CH)N=CH}-CHN-6-(OH)}](Cl) (9).
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