Preparation and hydrosilylation activity of a molybdenum carbonyl complex that features a pentadentate bis(imino)pyridine ligand

Raja Pal, Thomas L. Groy, Amanda C. Bowman, Ryan Trovitch

Research output: Contribution to journalArticle

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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, PyEtPDI, resulted in carbonyl ligand substitution and formation of the respective bis(ligand) compound ( PyEtPDI)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, Ph2PPrPDI, to 120 °C allowed for the preparation of (Ph2PPrPDI)Mo(CO) (2), which is supported by a κ5-N,N,N,P,P-Ph2PPrPDI 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.

Original languageEnglish
Pages (from-to)9357-9365
Number of pages9
JournalInorganic Chemistry
Volume53
Issue number17
DOIs
Publication statusPublished - Sep 2 2014

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Hydrosilylation
Molybdenum
molybdenum
pyridines
Ligands
preparation
ligands
phosphine
chelates
Carbon Monoxide
aldehydes
Aldehydes
phosphines
Density functional theory
pyridine
isolation
Substitution reactions
Single crystals
substitutes
density functional theory

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Preparation and hydrosilylation activity of a molybdenum carbonyl complex that features a pentadentate bis(imino)pyridine ligand. / Pal, Raja; Groy, Thomas L.; Bowman, Amanda C.; Trovitch, Ryan.

In: Inorganic Chemistry, Vol. 53, No. 17, 02.09.2014, p. 9357-9365.

Research output: Contribution to journalArticle

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