TpPtMe(H)₂:  Why Is There H/D Scrambling of the Methyl Group but Not Methane Loss?

The reactivity of TpPtMe(H)₂ (Tp = hydrido-tris(pyrazolyl)borate) was investigated. This complex is remarkably resistant to methane loss; heating it in methanol at 55 °C does not lead to either methane or hydrogen loss. When CD₃OD is used, reversible H/D scrambling of the hydrides and the methyl hydrogens occurs. This reactivity was investigated by density functional theory (DFT) methods at the mPW1k/LANL2DZ+P//mPW1k/LANL2DZ level. It was found that methane loss cannot occur due to the rigidity of the Tp ligand, which does not allow the trans geometry which would be required for the product of methane elimination, TpPtH. The resulting complex is very high in energy, and therefore the loss of methane is unfavorable. On the other hand, H/D scrambling of the methyl ligand is relatively facile. It proceeds through an η^2-CH-CH₄ complex, even though methane loss is not observed. The model system, [(NH₃)₃PtMe(H)₂]⁺ was examined to verify that the cause of the observations is the rigidity of the Tp system. The reaction was investigated at a number of levels of DFT. It was concluded that investigations of similar sized systems should be examined at the above level of theory or the mPW1k/SDB-cc-pVDZ//mPW1k/SDD level for improved accuracy of the energetic calculations.