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Título: | Addition of water across Si−Ir bonds in iridium complexes with κ-P,P,Si (biPSi) pincer ligands |
Autor: | García-Camprubí, Alba; Martín, Marta CSIC ORCID; Sola, Eduardo CSIC ORCID CVN | Fecha de publicación: | 2010 | Editor: | American Chemical Society | Citación: | Inorganic Chemistry 49(22): 10649-10657 (2010) | Resumen: | Electrophiles such as Me+, Ag+, or protons react with the five-coordinate Ir(III) complex [IrClH(biPSi)] (biPSi = κ-P,P,Si-Si(Me){(CH2)3PPh2}2) by abstracting its chloride ligand. The resulting species can be stabilized by a variety of L ligands to give the cationic complexes [IrH(biPSi)L2]+. The derivative [IrH(biPSi)(NCMe)2]+ has been subjected to a kinetic study regarding the facile dissociations of its acetonitrile ligands. The presence of water changes the course of the reaction producing dihydride complexes that contain the silanol ligand κ-O,P,P-HOSi(Me){(CH2)3PPh2}2 (biPSiOH). The water activation product [IrH2(biPSiOH)(NCMe)](CF3SO3) undergoes insertion reactions with ethylene and phenylacetylene. The use of hydrolyzable fluorinated counterions such as PF6− or BF4− further modifies the reaction by provoking the incorporation of fluoride at the silicon atom of the former biPSi ligand. The dihydride resulting after such a process, [IrH2(biPSiF)(NCMe)2]BF4 (biPSiF = κ-P2-FSi(Me){(CH2)3PPh2}2), displays a trans-chelating diphosphine ligand. When dehydrogenating the Ir center, spontaneously or using ethylene as hydrogen acceptor, the diphosphine backbone undergoes a Si−C bond cleavage leading to a new Ir(III) species with κ-P,Si and κ-C,P chelate ligands. | URI: | http://hdl.handle.net/10261/52269 | DOI: | 10.1021/ic1016774 | Identificadores: | doi: 10.1021/ic1016774 issn: 0020-1669 e-issn: 1520-510X |
Aparece en las colecciones: | (ICMA) Artículos |
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