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Szatkowski L, Hall MB. Molybdenum Trihydride Complexes: Computational Determinations of Hydrogen Positions and Rearrangement Mechanisms. Inorg Chem. 2015;54(13):6380-5doi: 10.1021/acs.inorgchem.5b00693.
Szatkowski, L., & Hall, M. B. (2015). Molybdenum Trihydride Complexes: Computational Determinations of Hydrogen Positions and Rearrangement Mechanisms. Inorganic chemistry, 54(13), 6380-5. https://doi.org/10.1021/acs.inorgchem.5b00693
Szatkowski, Lukasz, and Hall, Michael B. "Molybdenum Trihydride Complexes: Computational Determinations of Hydrogen Positions and Rearrangement Mechanisms." Inorganic chemistry vol. 54,13 (2015): 6380-5. doi: https://doi.org/10.1021/acs.inorgchem.5b00693
Szatkowski L, Hall MB. Molybdenum Trihydride Complexes: Computational Determinations of Hydrogen Positions and Rearrangement Mechanisms. Inorg Chem. 2015 Jul 06;54(13):6380-5. doi: 10.1021/acs.inorgchem.5b00693. Epub 2015 Jun 23. PMID: 26102430.
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Inorg Chem. 2015 Jul 06;54(13):6380-5. doi: 10.1021/acs.inorgchem.5b00693. Epub 2015 Jun 23.

Molybdenum Trihydride Complexes: Computational Determinations of Hydrogen Positions and Rearrangement Mechanisms.

Inorganic chemistry

Lukasz Szatkowski, Michael B Hall

PMID: 26102430 DOI: 10.1021/acs.inorgchem.5b00693

Abstract

In crystal structures of the molybdenum complexes [(1,2,4-C5H2(t)Bu3)Mo(PMe3)2H3] (Cp(t)Bu3) and [(C5H(i)Pr4)Mo(PMe3)2H3] (Cp(i)Pr4), the Mo-bound hydrogen positions were resolved for Cp(t)Bu3, but not for Cp(i)Pr4. NMR experiments revealed the existence of an unknown mechanism for hydrogen atom exchange in these molecules, which can be "frozen out" for Cp(t)Bu3 but not for Cp(i)Pr4. Density functional theory calculations of the most stable conformations for both complexes in the gas phase and in a continuum solvent model indicate that the H's of the Cp(i)Pr4 complex are unresloved because of their disorder, which does not occur for Cp(t)Bu3. A corresponding examination of alternative rearrangement pathways shows that the rearrangements of the H's could occur by two mechanisms: parallel to the cyclopentadienyl (Cp) ring in a single step and perpendicular to the Cp ring in two steps. The parallel pathway is preferred for both molecules, but it has a lower energy barrier for Cp(i)Pr4 than for Cp(t)Bu3.

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