TY - JOUR
T1 - Mechanistic studies on the interaction of [(κ3- P, P, P -NP3)IrH3] [NP3 = N(CH2CH 2PPh2)3] with HBF4 and Fluorinated Alcohols by Combined NMR, IR, and DFT Techniques
AU - Rossin, Andrea
AU - Gutsul, Evgenii I.
AU - Belkova, Natalia V.
AU - Epstein, Lina M.
AU - Gonsalvi, Luca
AU - Lledós, Agustí
AU - Lyssenko, Konstantin A.
AU - Peruzzini, Maurizio
AU - Shubina, Elena S.
AU - Zanobini, Fabrizio
PY - 2010/5/3
Y1 - 2010/5/3
N2 - 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.
AB - 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.
U2 - 10.1021/ic100313j
DO - 10.1021/ic100313j
M3 - Article
VL - 49
SP - 4343
EP - 4354
IS - 9
ER -