Synthesis, X-ray studies, and catalytic allylic amination reactions with ruthenium(IV) allyl carbonate complexes

Results from selected ruthenium-catalyzed allylic amination reactions, using a carbonate Ru-Cp* (or Cp) allyl cationic precursor, are reported. With a phenyl-substituted allyl substrate as the starting material, the rates of the amination reactions, as well as the regioselectivity, are shown to depend on the structure of the allyl substrate, the amine nucleophile, and the solvent. Two new Ru-allyl carbonate complexes are reported, as well as the solid-state structure for the new carbonate salt [Ru(Cp)(O2C{OBu'})(eta(3)-PhCHCHCH2)](PF6). A number of aniline- and substrate-related Cp* and Cp eta(6)-arene complexes of Ru(II) are described

Bonding in palladium(II) and platinum(II) allyl MeO- and H-MOP complexes. Subtle differences via C-13 NMR

C-13 NMR studies have shown that in both Pd(II)- and Pt(II)-allyl (modified-MOP) (MOP = (S)-2-diarylphosphino-1,1'-binaphthyl) complexes the substituent on the MOP auxiliary can affect how the naphthyl backbone interacts with a metal center. With the MeO-MOP analogue, the metal binds the carbon in a weak eta(1)-fashion, whereas with H-MOP it prefers an eta(2)-binding mode. For the Pt complexes, the (1)J(Pt-195,C-13) values proved to be diagnostic tools. Both modes of bonding afford relatively weak bonds to the metal. Modifying the MOP ligand structure from a PPh2 to a P(3,5-di-tert-butylphenyl)2 analogue can markedly affect the bond distances within the coordination sphere, as indicated by the X-ray structural data for PdCl(eta(3)-C3H5)(modified-MOP). 2-D NMR exchange spectroscopy can be used to recognize and distinguish between the two most common types of eta(3)-eta(1)-eta(3) isomerization process, i.e., rotation around the allyl C-C bond versus rotation around the allyl M-C bond. For the complex PdCl(eta(3)-C3H5)(H-MOP), the fastest isomerization process involves rotation around the allyl C-C bond

X-ray, C-13 NMR, and DFT studies on a ruthenium(IV) allyl complex. Explanation for the observed control of regioselectivity in allylic alkylation chemistry

X-ray, C-13 NMR, and DFT studies on the cationic Ru(IV) allyl complex Ru(Cp*)Cl(CH3CN)(eta(3)- PhCHCHCH2), as a PF6 salt, have revealed a marked asymmetry in the bonding of the allyl ligand, which can be interpreted as arising from differences in T-bonding from the metal center to the two terminal allyl carbons. This asymmetry in the bonding is offered as an explanation for the observed control of regioselectivity in the Ru-catalyzed allylic alkylation reaction