Mechanistic studies on the interaction of [(κ<sup>3</sup>- P, P, P -NP<inf>3</inf>)IrH<inf>3</inf>] [NP<inf>3</inf> = N(CH<inf>2</inf>CH <inf>2</inf>PPh<inf>2</inf>)<inf>3</inf>] with HBF<inf>4</inf> and Fluorinated Alcohols by Combined NMR, IR, and DFT Techniques

Andrea Rossin, Evgenii I. Gutsul, Natalia V. Belkova, Lina M. Epstein, Luca Gonsalvi, Agustí Lledós, Konstantin A. Lyssenko, Maurizio Peruzzini, Elena S. Shubina, Fabrizio Zanobini

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15 Citations (Scopus)

Abstract

The novel iridium(III) hydride [(κ3-P,P,P-NP 3)IrH3] [NP3 = N(CH2CH 2PPh2)3] was synthesized and characterized by spectroscopic methods and X-ray crystallography. Its reactivity with strong (HBF4) and medium-strength [the fluorinated alcohols 1,1,1-trifluoroethanol (TFE) and 1,1,1,3,3,3-hexafluoroisopropanol (HFIP)] proton donors was investigated through low-temperature IR and multinuclear NMR spectroscopy. In the case of the weak acid TFE, the only species observed in the 190-298 K temperature range was the dihydrogen-bonded adduct between the hydride and the alcohol, while with the stronger acid HBF4, the proton transfer was complete, giving rise to a new intermediate [(κ3-P,P,P-NP3)IrH4]+. With a medium-strength acid like HFIP, two different sets of signals for the intermediate species were observed besides dihydrogen bond formation. In all cases, the final reaction product at ambient temperature was found to be the stable dihydride [(κ4-NP3)IrH2] +, after slow molecular dihydrogen release. The nature of the short-living species was investigated with the help of density functional theory calculations at the M05-2X//6-31++G(df,pd) level of theory. © 2010 American Chemical Society.
Original languageEnglish
Pages (from-to)4343-4354
JournalInorganic Chemistry
Volume49
Issue number9
DOIs
Publication statusPublished - 3 May 2010

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