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

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.

Reaction of HSi(OEt)3 with IrCl(CO)(PPh3)2 produces IrCl(H){Si(OEt)3}(CO)(PPh3)2 (1) at room temperature or IrCl(H)2(CO)(PPh3)2 (2) at 50 °C depending on the reaction temperatures, whereas the reaction of HSiEt3 with IrCl(CO)(PPh3)2 yields Ir(H)2(SiEt3)(CO)(PPh3)2 (4) via an elimination of ClSiEt3.Figure optionsDownload as PowerPoint slide