Comparative reactivity of triorganosilanes, HSi(OEt)3 and HSiEt3, with IrCl(CO)(PPh3)2. Formation of IrCl(H)2(CO)(PPh3)2 or Ir(H)2(SiEt3)(CO)(PPh3)2 depending on the substituents at Si |
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| Authors: | Yasushi Nishihara Miwa Takemura |
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| Institution: | a Division of Chemistry and Biochemistry, Graduate School of Natural Science and Technology, Okayama University, 3-1-1 Tsushimanaka, Okayama 700-8530, Japan
b Chemical Resources Laboratory, Tokyo Institute of Technology, R1-03, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan |
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| Abstract: | Reaction of HSi(OEt)3 with IrCl(CO)(PPh3)2 (5:1 molar ratio) at room temperature for 1 h gives IrCl(H){Si(OEt)3}(CO)(PPh3)2 (1), which is observed by the 1H and 31P{1H} NMR spectra of the reaction mixture. The same reaction, but in 20:1 molar ratio at 50 °C for 24 h produces IrCl(H)2(CO)(PPh3)2 (2) rather than the expected product Ir(H)2{Si(OEt)3}(CO)(PPh3)2 (3) that was previously reported to be formed by this reaction. Accompanying formation of Si(OEt)4, (EtO)3SiOSi(OEt)3, and (EtO)2HSiOSi(OEt)3 is observed. On the other hand, trialkylhydrosilane HSiEt3 reacts with IrCl(CO)(PPh3)2 (10:1 molar ratio) at 80 °C for 84 h to give Ir(H)2(SiEt3)(CO)(PPh3)2 (4) in a high yield, accompanying with a release of ClSiEt3. |
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| Keywords: | Iridium Hydrosilanes Oxidative addition Hydrido complex |
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