Pseudo-tetrahedral Rhodium and Iridium Complexes: Catalytic Synthesis ofE-Enynes

Autor:	José A. López, Miguel A. Ciriano, Alejandro Julián, Cristina Tejel, Ana M. Geer
Přispěvatelé:	Ministerio de Economía, Industria y Competitividad (España), Agencia Estatal de Investigación (España), Gobierno de Aragón, European Commission, Ministerio de Economía y Competitividad (España)
Rok vydání:	2018
Předmět:	chemistry.chemical_classification 010405 organic chemistry Chemistry Organic Chemistry Alkyne Regioselectivity chemistry.chemical_element General Chemistry 010402 general chemistry 01 natural sciences Medicinal chemistry Catalysis 0104 chemical sciences Rhodium chemistry.chemical_compound Reactivity (chemistry) Iridium Acetonitrile Hydrometalation
Zdroj:	Digital.CSIC. Repositorio Institucional del CSIC instname
ISSN:	0947-6539
DOI:	10.1002/chem.201803878
Popis:	Dedicated in Memoriam to Professor Dr. Pascual Royo. The reactions of the rhodium(I) and iridium(I) complexes [M(PhBP3)(C2H4)(NCMe)] (PhBP3=PhB(CH2PPh2)3−) with alkynes have resulted in the synthesis of a new family of pseudo‐tetrahedral complexes, [M(PhBP3)(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=PMe3, CNtBu) 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(PhBP3)(C2H4)(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. The generous financial support from the MINECO/FEDER (Projects CTQ2014‐53033‐P and CTQ2017‐83421‐P, C.T.) and the Gobierno de Aragón/FEDER (GA/FEDER, Inorganic Molecular Architecture Group E08_17R; C.T.) is gratefully acknowledged.
Databáze:	OpenAIRE
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