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Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
Published on: May 28, 2014
Silica-Supported Mononuclear Methyl-Platinum Complexes Stabilized by Trimethylphosphine-Synthesis, Structure, and
Lea S Kopietz1, Sven Schaefer2, Oksana Storcheva1
1Department of Chemistry, TUM School of Natural Sciences, and Catalysis Research Center, Technical University of Munich, Garching, Germany.
This study synthesizes a platinum surface complex, revealing a stabilized platinum hydride catalyst. This contrasts with other complexes that form nanoparticles, offering new insights into single-site platinum chemistry.
Area of Science:
- Heterogeneous catalysis
- Organometallic chemistry
- Surface science
Background:
- The surface chemistry of single-site platinum complexes with phosphine ligands is less understood than their solution-phase counterparts.
- Supported platinum catalysts are crucial in various chemical transformations.
- Stabilizing single-site platinum complexes on supports is key for controlled reactivity.
Purpose of the Study:
- To synthesize and characterize a supported bis(phosphine)methylplatinum(II) complex on silicon dioxide.
- To investigate the reactivity of this complex with small molecules (CO, H2) and under inert conditions.
- To compare the stability and reactivity of this phosphine-ligated complex with other supported platinum methyl complexes.
Main Methods:
- Synthesis of PtMe(PMe3)2/SiO2 complex.
- Characterization using Infrared (IR) spectroscopy, solid-state Nuclear Magnetic Resonance (NMR) spectroscopy, and X-ray absorption spectroscopy (XAS).
- Reactivity studies involving carbon monoxide, hydrogen, and inert gas exposure.
Main Results:
- Successful synthesis and characterization of the supported bis(phosphine)methylplatinum(II) complex.
- Formation of several isolated trans complexes on silica, stabilized by phosphine ligands.
- Identification of a platinum hydride intermediate that effectively catalyzes 1-hexene isomerization.
- Demonstration of enhanced stability of the molecular hydride compared to nanoparticle formation observed with other complexes.
Conclusions:
- Sterically non-demanding phosphine ligands stabilize platinum centers on silica, enabling the formation of well-defined single-site complexes.
- The stabilized platinum hydride exhibits catalytic activity for alkene isomerization.
- This phosphine-ligated system offers a more stable alternative to previously studied supported platinum methyl complexes, avoiding nanoparticle formation under mild conditions.
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