Efficient and chemoselective hydroboration of organic nitriles promoted by TiIV catalyst supported by unsymmetrical acenaphthenequinonediimine ligand

Banerjee, Indrani and Anga, Srinivas and Panda, Tarun K (2019) Efficient and chemoselective hydroboration of organic nitriles promoted by TiIV catalyst supported by unsymmetrical acenaphthenequinonediimine ligand. Journal of Organometallic Chemistry. p. 120958. ISSN 0022328X

Full text not available from this repository. (Request a copy)

Abstract

We report the synthesis, characterization, and utilization of a titanium (IV) complex [(η5-C5H5){L}TiCl2] (1) supported by a monoanionic ligand (L), N-(2, 6-diisopropyl)acenaphthenequinonediimido, as a molecular pre-catalyst for the hydroboration of nitriles. The unsymmetrical N-silylated N-(2, 6-diisopropyl)-N-(trimethylsilyl)-acenaphthenequinonediimine ligand (LSiMe3) was obtained upon the completion of a one-pot reaction between N-(2, 6-diisopropyl)iminoacenaphthenone and lithium hexamethyldisilazide in the presence of trimethylsilyl chloride in 1:1:1 M ratio at room temperature. The reaction of LSiMe3 with { η5-(C5H5)TiCl3) in equal proportion (1:1) at 60 °C afforded the titanium complex [(η5-C5H5){L}TiCl2] (1) in good yield. The molecular structures of the N-silyl ligand (LSiMe3) and Ti(IV) complex 1 were established by single-crystal X-ray analysis. Complex 1 was tested as a pre-catalyst for hydroboration of nitriles with pinacolborane (HBpin) and catecholborane (HBcat) to afford diboryl amines at ambient temperature. Titanium complex 1 exhibited high conversion, superior selectivity, and broad functional group tolerance during hydroboration of nitriles with both HBpin and HBcat under mild conditions.

[error in script]

IITH Creators: