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Rossin A, Gutsul EI, Belkova NV, et al. Mechanistic studies on the interaction of [(kappa3-P,P,P-NP3)IrH3] [NP3 = N(CH2CH2PPh2)3] with HBF4 and fluorinated alcohols by combined NMR, IR, and DFT techniques. Inorg Chem. 2010;49(9):4343-54doi: 10.1021/ic100313j.
Rossin, A., Gutsul, E. I., Belkova, N. V., Epstein, L. M., Gonsalvi, L., Lledós, A., Lyssenko, K. A., Peruzzini, M., Shubina, E. S., & Zanobini, F. (2010). Mechanistic studies on the interaction of [(kappa3-P,P,P-NP3)IrH3] [NP3 = N(CH2CH2PPh2)3] with HBF4 and fluorinated alcohols by combined NMR, IR, and DFT techniques. Inorganic chemistry, 49(9), 4343-54. https://doi.org/10.1021/ic100313j
Rossin, Andrea, et al. "Mechanistic studies on the interaction of [(kappa3-P,P,P-NP3)IrH3] [NP3 = N(CH2CH2PPh2)3] with HBF4 and fluorinated alcohols by combined NMR, IR, and DFT techniques." Inorganic chemistry vol. 49,9 (2010): 4343-54. doi: https://doi.org/10.1021/ic100313j
Rossin A, Gutsul EI, Belkova NV, Epstein LM, Gonsalvi L, Lledós A, Lyssenko KA, Peruzzini M, Shubina ES, Zanobini F. Mechanistic studies on the interaction of [(kappa3-P,P,P-NP3)IrH3] [NP3 = N(CH2CH2PPh2)3] with HBF4 and fluorinated alcohols by combined NMR, IR, and DFT techniques. Inorg Chem. 2010 May 03;49(9):4343-54. doi: 10.1021/ic100313j. PMID: 20377258.
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Inorg Chem. 2010 May 03;49(9):4343-54. doi: 10.1021/ic100313j.

Mechanistic studies on the interaction of [(kappa3-P,P,P-NP3)IrH3] [NP3 = N(CH2CH2PPh2)3] with HBF4 and fluorinated alcohols by combined NMR, IR, and DFT techniques.

Inorganic chemistry

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

Affiliations

  1. Instituto di Chimica dei Composti Organometallici (ICCOM-CNR), Via Madonna del Piano 10, 50019 Sesto Fiorentino (Firenze), Italy.

PMID: 20377258 DOI: 10.1021/ic100313j

Abstract

The novel iridium(III) hydride [(kappa(3)-P,P,P-NP(3))IrH(3)] [NP(3) = N(CH(2)CH(2)PPh(2))(3)] was synthesized and characterized by spectroscopic methods and X-ray crystallography. Its reactivity with strong (HBF(4)) 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 HBF(4), the proton transfer was complete, giving rise to a new intermediate [(kappa(3)-P,P,P-NP(3))IrH(4)](+). 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 [(kappa(4)-NP(3))IrH(2)](+), 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.

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