Synthesis and reactivity of an isolable cobalt(I) complex containing a β-diketiminate-based acyclic tetradentate ligand

Elodie E. Marlier, Bridget A. Ulrich, Kristopher McNeill

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9 Scopus citations

Abstract

A model for cobalamin was synthesized using a new monoanionic tetradentate nitrogen donor ligand; 2-(4- tolyl)-1,3-bis(2-isopropylpyridyl)propenediimine (Tol- BDI (2-pp)2H) (1), which utilizes isopropylpyridines as pendant arms on a β-diketiminate (BDI) backbone. During the synthesis of 1, the rearrangement product, Tol-BDI (2-pp)(4-pp)H (2) was observed. Metalation of 1 with zinc iodide and cobalt chloride yielded the corresponding Tol-BDI (2-pp)2ZnI (3) and Tol-BDI (2-pp)2CoCl (4) complexes. The redox properties of 4 in comparison to cobalamin were examined through electrochemical studies. Electrochemical and bulk reduction of complex 4 gave a diamagnetic cobalt(I) complex, Tol-BDI (2-pp)2Co (5). Reactivity of 5 toward C-X bonds was investigated using methyl iodide and 1-iodo-2-(trimethylsilyl)acetylene, yielding Tol-BDI (2-pp)2Co(CH 3)I and Tol-BDI (2-pp)2Co(C 2Si(CH 3) 3)I respectively. Synthesis and characterization details for these complexes, including the crystal structure of 3, are reported.

Original languageEnglish (US)
Pages (from-to)2079-2085
Number of pages7
JournalInorganic chemistry
Volume51
Issue number4
DOIs
StatePublished - Feb 20 2012

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