Details

Autor(en) / Beteiligte

• Gelabert, Ricard
• Moreno, Miquel
• Lluch, José M
• Lledós, Agustí
• Pons, Vincent
• Heinekey, D. Michael

Titel

Synthesis and Properties of Compressed Dihydride Complexes of Iridium:  Theoretical and Spectroscopic Investigations

Ist Teil von

• Journal of the American Chemical Society, 2004-07, Vol.126 (28), p.8813-8822

Ort / Verlag

Washington, DC: American Chemical Society

Erscheinungsjahr

2004

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Reaction of [Cp*Ir(P−P)Cl][B(C6F5)4] (P−P = bisdimethydiphosphinomethane (dmpm), bisdiphenyldiphosphinomethane (dppm)) with [Et3Si][B(C6F5)4] in methylene chloride under 1 atm of hydrogen gas affords the dicationic compressed dihydride complexes [Cp*Ir(P−P)H2][B(C6F5)4]2. These dicationic complexes are highly acidic and are very readily deprotonated to the corresponding monohydride cations. When the preparative reaction is carried out under HD gas, the hydride resonance exhibits J HD = 7−9 Hz, depending upon the temperature of observation, with higher values of J HD observed at higher temperatures. A thermally labile rhodium analogue, [Cp*Rh(dmpm)(H2)][B(C6F5)4]2, was prepared similarly. A sample prepared with HD gas gave J HD = 31 Hz and J HRh = 31 Hz, allowing the Rh complex to be identified as a dihydrogen complex. Quantum dynamics calculations on a density functional theory (DFT) potential energy surface have been used to explore the structure of the Ir complexes, with particular emphasis on the nature of the potential energy surface governing the interaction between the two hydride ligands and the Ir center.