TY - JOUR
T1 - Synthesis and Surface Attachment of Molecular Re(I) Hydride Species with Silatrane Functionalized Bipyridyl Ligands
AU - Jia, Xiaofan
AU - Cui, Kai
AU - Alvarez-Hernandez, Jose L.
AU - Donley, Carrie L.
AU - Gang, Albert
AU - Hammes-Schiffer, Sharon
AU - Hazari, Nilay
AU - Jeon, Sungho
AU - Mayer, James M.
AU - Nedzbala, Hannah S.
AU - Shang, Bo
AU - Stach, Eric A.
AU - Stewart-Jones, Eleanor
AU - Wang, Hailiang
AU - Williams, Alexa
N1 - Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/8/28
Y1 - 2023/8/28
N2 - Three molecular Re hydrides of the form (Rbpy)Re(CO)3H with 2,2′-bipyridine (bpy) ligands containing silatrane functional groups for surface attachment on metal oxide surfaces were synthesized. IR spectroscopy and cyclic voltammetry (CV) demonstrated that the complexes containing the silatrane functional groups have electronic properties similar to those of a control compound, which did not contain functional groups for attachment. Additionally, in a similar fashion to the control compound, the silatrane containing Re hydrides are electrocatalysts for the reduction of CO2 to CO in solution. The silatrane containing complexes were immobilized on a thin layer of TiO2 on Si, and the resulting composites were characterized using X-ray photoelectron and IR spectroscopy as well as cyclic voltammetry in the dark and under illumination. Control experiments indicated that the hydride complexes are not stable on the surface and degrade to species which contain a bpy ligand, three CO ligands, and an unknown ligand in the sixth site. Similarly, when one of the silatrane containing Re hydride complexes was immobilized on Si nanoparticles with a thin layer of SiO2 or silica nanoparticles, the hydride ligand was lost. Density functional theory calculations were used to corroborate the observed behavior of hydride species on a surface. Overall, this work demonstrates the difficulties associated with attaching well-defined molecular hydride complexes to metal oxide surfaces.
AB - Three molecular Re hydrides of the form (Rbpy)Re(CO)3H with 2,2′-bipyridine (bpy) ligands containing silatrane functional groups for surface attachment on metal oxide surfaces were synthesized. IR spectroscopy and cyclic voltammetry (CV) demonstrated that the complexes containing the silatrane functional groups have electronic properties similar to those of a control compound, which did not contain functional groups for attachment. Additionally, in a similar fashion to the control compound, the silatrane containing Re hydrides are electrocatalysts for the reduction of CO2 to CO in solution. The silatrane containing complexes were immobilized on a thin layer of TiO2 on Si, and the resulting composites were characterized using X-ray photoelectron and IR spectroscopy as well as cyclic voltammetry in the dark and under illumination. Control experiments indicated that the hydride complexes are not stable on the surface and degrade to species which contain a bpy ligand, three CO ligands, and an unknown ligand in the sixth site. Similarly, when one of the silatrane containing Re hydride complexes was immobilized on Si nanoparticles with a thin layer of SiO2 or silica nanoparticles, the hydride ligand was lost. Density functional theory calculations were used to corroborate the observed behavior of hydride species on a surface. Overall, this work demonstrates the difficulties associated with attaching well-defined molecular hydride complexes to metal oxide surfaces.
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U2 - 10.1021/acs.organomet.3c00235
DO - 10.1021/acs.organomet.3c00235
M3 - Article
AN - SCOPUS:85169159859
SN - 0276-7333
VL - 42
SP - 2238
EP - 2250
JO - Organometallics
JF - Organometallics
IS - 16
ER -