A series of phosphine-diimine ligands were synthesized by the condensation of 2-(diphenylphosphino)aniline (PNH2) with a variety of formyl and ketopyridines. Condensation of PNH2 with acetyl- and benzoylpyridine yielded the Ph2P(C6H4)N=C(R)(C5H4N), respectively abbreviated PNMepy and PNPhpy. With ferrous halides, PNPhpy gave the complexes FeX2(PNPhpy) (X = Cl, Br). Condensation of pyridine carboxaldehyde and its 6-methyl derivatives with PNH2 was achieved using a ferrous template, affording low-spin complexes [Fe(PNHpyR)2]2+ (R = H, Me). Dicarbonyls Fe(PNRpy)(CO)2 were produced by treating PNMepy with Fe(benzylideneacetone)(CO)3 and reduction of FeX2(PNPhpy) with NaBEt3H under a CO atmosphere. Cyclic voltammetric studies show that the [FeL3(CO)2]0/- and [FeL3(CO)2]+/0 couples are similar for a range of tridentate ligands, but the PNPhpy system uniquely sustains two one-electron reductions. Treatment of Fe(PNPhpy)X2 with NaBEt3H gave active catalysts for the hydroboration of 1-octene with pinacolborane. Similarly, these catalysts proved active for the addition of diphenylsilane, but not HSiMe(OSiMe3)2, to 1-octene and vinylsilanes. Evidence is presented that catalysis occurs via iron hydride complexes of intact PNPhpy.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry