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

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journal contribution
posted on 2004-07-21, 00:00 authored by Ricard Gelabert, Miquel Moreno, José M. Lluch, Agustí Lledós, Vincent Pons, D. Michael Heinekey
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 JHD = 7−9 Hz, depending upon the temperature of observation, with higher values of JHD 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 JHD = 31 Hz and JHRh = 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.