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Preparation and Hydrosilylation Activity of a Molybdenum Carbonyl Complex That Features a Pentadentate Bis(imino)pyridine Ligand
- Source :
- Inorganic Chemistry. 53:9357-9365
- Publication Year :
- 2014
- Publisher :
- American Chemical Society (ACS), 2014.
-
Abstract
- Attempts to prepare low-valent molybdenum complexes that feature a pentadentate 2,6-bis(imino)pyridine (or pyridine diimine, PDI) chelate allowed for the isolation of two different products. Refluxing Mo(CO)6 with the pyridine-substituted PDI ligand, (PyEt)PDI, resulted in carbonyl ligand substitution and formation of the respective bis(ligand) compound ((PyEt)PDI)2Mo (1). This complex was investigated by single-crystal X-ray diffraction, and density functional theory calculations indicated that 1 possesses a Mo(0) center that back-bonds into the π*-orbitals of the unreduced PDI ligands. Heating an equimolar solution of Mo(CO)6 and the phosphine-substituted PDI ligand, (Ph2PPr)PDI, to 120 °C allowed for the preparation of ((Ph2PPr)PDI)Mo(CO) (2), which is supported by a κ(5)-N,N,N,P,P-(Ph2PPr)PDI chelate. Notably, 1 and 2 have been found to catalyze the hydrosilylation of benzaldehyde at 90 °C, and the optimization of 2-catalyzed aldehyde hydrosilylation at this temperature afforded turnover frequencies of up to 330 h(-1). Considering additional experimental observations, the potential mechanism of 2-mediated carbonyl hydrosilylation is discussed.
Details
- ISSN :
- 1520510X and 00201669
- Volume :
- 53
- Database :
- OpenAIRE
- Journal :
- Inorganic Chemistry
- Accession number :
- edsair.doi.dedup.....6ae6c73a92484c9ee038f96c1f394c04