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• W2890957728 endingPage "17556" @default.
• W2890957728 startingPage "17545" @default.
• W2890957728 abstract "Abstract The reactions of the rhodium(I) and iridium(I) complexes [M(PhBP 3 )(C 2 H 4 )(NCMe)] (PhBP 3 =PhB(CH 2 PPh 2 ) 3 − ) with alkynes have resulted in the synthesis of a new family of pseudo‐tetrahedral complexes, [M(PhBP 3 )(RC≡CR′)] (M=Rh, Ir), which contain the alkyne as a four‐electron donor. The reactions of these unusual compounds with two‐electron donors (L=PMe 3 , CN t Bu) produced a change in the “donicity” of the alkyne from a 4e − to a 2e − donor to give five‐coordinate complexes. These were the final products with the iridium complexes, whereas further reactions took place with the rhodium complexes. In particular, C(sp)−H bond activation of the alkyne occurred leading to hydrido alkynyl complexes. This process is essential for the further reactivity of the alkynes, and if the alkyne itself was used as reagent, E ‐enyne complexes were obtained. As a consequence of this chemistry, we show that the complex [Rh(PhBP 3 )(C 2 H 4 )(NCMe)] is a very efficient pre‐catalyst for the regioselective di‐ and trimerization of terminal alkynes to E ‐enynes and benzene derivatives, respectively. Interestingly, acetonitrile significantly enhanced the catalytic activity by facilitating the C(sp)−H bond activation step. A hydrometalation mechanism to account for these experimental observations is proposed." @default.
• W2890957728 created "2018-09-27" @default.
• W2890957728 creator A5006451125 @default.
• W2890957728 creator A5031291421 @default.
• W2890957728 creator A5062304473 @default.
• W2890957728 creator A5065885946 @default.
• W2890957728 creator A5079818941 @default.
• W2890957728 date "2018-11-05" @default.
• W2890957728 modified "2023-10-14" @default.
• W2890957728 title "Pseudo-tetrahedral Rhodium and Iridium Complexes: Catalytic Synthesis of<i>E</i>-Enynes" @default.
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