Stabilizing Terminal Ni(III)–Hydroxide Complex Using NNN-Pincer Ligands: Synthesis and Characterization
- Jitendrasingh Rajpurohit (5497955)
- Pragya Shukla (4891924)
- Pardeep Kumar (604685)
- Chinmoy Das (4557622)
- Shefali Vaidya (3129192)
- Mahesh Sundararajan (1431223)
- Muralidharan Shanmugam (1404973)
- Maheswaran Shanmugam (1891309)
DOIAbstract
The reaction of [Ni(COD)2] (COD; cyclooctadiene) in THF with the NNN-pincer ligand bis(imino)pyridyl (L1) reveals a susceptibility to oxidation in an inert atmosphere ([O2] level <0.5 ppm), resulting in a transient Ni:dioxygen adduct. This reactive intermediate abstracts a hydrogen atom from THF and stabilizes an uncommon Ni(III) complex. The complex is crystallographically characterized by a molecular formula of [NiIII(L1··)2–(OH)] (1). Various isotopically labeled experiments (16O/18O) assertively endorse the origin of terminal oxygen based ligand in 1 due to the activation of molecular dioxygen. The presence of proton bound to the terminal oxygen in 1 is well supported by NMR, IR spectroscopy, DFT calculations, and hydrogen atom tran...
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