124602-43-3Relevant articles and documents
Stereospecific, sequential carbonyl insertion and extrusion reactions. Preparation and characterization of [Fe(diars)(Lα)(CO)2 (CH3)]+ and [Fe(diars)(Lα)(Lβ)(CO) (C(O)CH3)ΡN+ complexes
Jablonski,Wang
, p. 318 - 428 (2008/10/08)
A series of σ-alkyl octahedral Fe(II) complexes, 9, of the form [Fe(diars)(CO)2(Lα)(CH3)]+ (diars = o-phenylenebis(dimethylarsine)) was stereospecifically prepared by thermal extrusion of carbon monoxide from the corresponding acyl derivatives. Migratory carbon monoxide insertion of 9 in the presence of a second phosphorus ligand, Lβ, afforded the isosteric acyl complexes [Fe(diars)(CO)(Lα)(Lβ)(C(O)CH3)]+ (15). The strong trans-labilizing effect of σ-acyl is proposed to account for the stereochemistry observed. Equilibrium constants for 9 ? 15 are a function of the total steric demand of Lα and Lβ. Diastereotopic phosphine substituents (Lα or Lβ = L = PR′2R″) were detected with use of 1H NMR spectroscopy, which indicates that the chiral Fe atom is configurationally stable on the 80- and 300-MHz 1H NMR time scales.