Iridium(I) complex of chelating pyridine-2-thiolate ligand: Synthesis, reactivity, and application to the catalytic E-selective terminal alkyne dimerization via C-H activation |
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| Authors: | Kenichi Ogata Akinori Toyota |
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| Institution: | Graduate School of Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Naka-cho, Koganei-shi, Tokyo 184-8588, Japan |
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| Abstract: | A novel iridium(I) complex bearing a chelate-coordinated pyridine-2-thiolate ligand Ir(η2-SNC5H4)(PPh3)2] (2) was prepared by the reaction of iridium ethylene complex IrCl(C2H4)(PPh3)2] (1) with lithium salt of pyridine-2-thiol (LiSNC5H4]). On the treatment of iridium(I) complex 2 with chloroform, iridium(III) dichloro-complex IrCl2(η2-SNC5H4)(PPh3)2] (3) was formed. Reactions of complex 2 with methyldiphenylsilane, acetic acid, and p-tolylacetylene afforded iridium(III) hydride complexes IrH(SiMePh2)(η2-SNC5H4)(PPh3)2] (4), IrH(O2CCH3)(η2-SNC5H4)(PPh3)2] (5), and IrH(C C(p-tolyl))(η2-SNC5H4)(PPh3)2] (6), respectively. Complex 2 catalyzed dimerization of terminal alkynes leading to enynes (7) with high E-selectivity via C-H bond activation. |
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| Keywords: | Iridium complex Pyridine-2-thiolate Hydride complex Dimerization of alkyne |
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