Reactivity of Ir(i)-aminophosphane platforms towards oxidants

Palmese, Marco ; Pérez-Torrente, Jesús J. (Universidad de Zaragoza) ; Passarelli, Vincenzo

Resumen: The iridium(I)-aminophosphane complex [Ir{κ3C,P,P′-(SiNP-H)}(cod)] has been prepared by reaction of [IrCl(cod)(SiNP)] with KCH3COO. DFT calculations show that this reaction takes place through an unexpected outer sphere mechanism (SiNP = SiMe2{N(4-C6H4Me)PPh2}2; SiNP-H = CH2SiMe{N(4-C6H4Me)PPh2}2). The reaction of [IrCl(cod)(SiNP)] or [Ir{κ3C,P,P′-(SiNP-H)}(cod)] with diverse oxidants has been explored, yielding a range of iridium(III) derivatives. On one hand, [IrCl(cod)(SiNP)] reacts with allyl chloride rendering the octahedral iridium(III) derivative [IrCl2(η3-C3H5)(SiNP)], which, in turn, reacts with tert-butyl isocyanide yielding the substitution product [IrCl(η3-C3H5)(CNtBu)(SiNP)]Cl via the observed intermediate [IrCl2(η1-C3H5)(CNtBu)(SiNP)]. On the other hand, the reaction of [Ir{κ3C,P,P′-(SiNP-H)}(cod)] with [FeCp2]X (X = PF6, CF3SO3), I2 or CF3SO3CH3 results in the metal-centered two-electron oxidation rendering a varied assortment of iridium(III) compounds. [Ir{κ3C,P,P′-(SiNP-H)}(cod)] reacts with [FeCp2]+ (1 : 2) in acetonitrile affording [Ir{κ3C,P,P′-(SiNP-H)}(CH3CN)3]2+ isolated as both the triflato and the hexafluorophosphato derivatives. Also, the reaction of [Ir{κ3C,P,P′-(SiNP-H)}(cod)] with I2 (1 : 1) yields a mixture of iridium(III) derivatives, namely the mononuclear compound [IrI(κ2P,P′-SiNP)(η2,η3-C8H11)]I, containing the η2,η3-cycloocta-2,6-dien-1-yl ligand, and two isomers of the dinuclear derivative [Ir2{κ3C,P,P′-(SiNP-H)}2(μ-I)3]I, the first species being isolated in low yield. DFT calculations indicate that [IrI(κ2P,P′-SiNP)(η2,η3-C8H11)]I forms as the result of a bielectronic oxidation of iridium(I) followed by the deprotonation of the cod ligand by iodide and the protonation of the methylene moiety of the [Ir{κ3C,P,P′-(SiNP-H)}] platform by the newly formed HI. Finally, the oxidation of [Ir{κ3C,P,P′-(SiNP-H)}(cod)] by methyl triflate proceeds via a hydride abstraction from the cod ligand, with the elimination of methane and the formation of the η2,η3-cycloocta-2,6-dien-1-yl ligand with the concomitant two-electron oxidation of the iridium centre. The crystal structures of selected compounds have been determined.

Idioma: Inglés

DOI: 10.1039/d3dt02361c

Año: 2023

Publicado en: Dalton Transactions 52, 38 (2023), 13689-13703
ISSN: 1477-9226

Factor impacto JCR: 3.5 (2023)

Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 13 / 44 = 0.295 (2023) - Q2 - T1

Factor impacto CITESCORE: 6.6 - Inorganic Chemistry (Q2)

Factor impacto SCIMAGO: 0.697 - Inorganic Chemistry (Q1)

Financiación: info:eu-repo/grantAgreement/ES/DGA/E42-23R
Financiación: info:eu-repo/grantAgreement/ES/MICINN-FEDER/PID2019-103965GB-I00

Tipo y forma: Artículo (Versión definitiva)

Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)