Insights in Mo (di)hydride bonds with ETS-NOCV

Ets nocv ts moh3

Bonding interactions in non-classical hydride/dihydrogen molybdocenes and their interconversion to trihydrides have been analyzed with ETS-NOCV in a recent inside-cover featured article. Ansa-bridges with a small bite angle make the Mo center more sterically available, favoring the non-classical hydride/dihydrogen complex for [(C5H4)2CMe2MoH(H2)]+ complexes. On the other hand, the trihydride configuration is favored for the less accesible Mo in ansa-bridged complexes with a heavier central atom (Si, Ge, Sn, Pb).

In [(C5H4)2CMe2MoH(H2)]+ the trihydride is a low-lying TS for hydrogen exchange. The ETS-NOCV analysis shows that the orbital interactions are much more favorable in the trihydride TS, almost fully counteracting the strongly increased steric repulsion in the TS.

Right: Energy decomposition analysis of Mo trihydride and TS for hydrogen exchange. Left: ETS-NOCV deformation density of the most important interactions in the TS for the hydrogen exchange reaction.

See also: Web presentation on ETS-NOCV by Mariusz Mitoraj.

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