Rhodium(I) complexes of α-keto-stabilised 1,2-bis(diphenylphosphino)alkane mono ylides
Rhodium(I) complexes of the hybrid ylide-phosphine ligands, Ph2P(CH2)nPPh2(CHC(O)C6H5) (n = 1: dppm-yl, or 2: dppe-yl) have been synthesised from [Rh(μ-C1)(COD)]2 (COD = 1,5-cyclooctadiene) and characterized by NMR spectroscopic and X-ray structural methods. The dppe-yl behaves as an ambidentate ligand; it functions as a monodentate P-donor ligand with a dangling ylidic carbon in the neutral chloro complex, [(COD)Rh(Cl)(dppe-yl)] (1), whereas replacement of the chloride by a non-coordinating counter anion results in the formation of the complexes, [(COD)Rh(L-L’)]+ (L-L’ = dppe-yl (2) or dppm-yl (3)) respectively in which the ligands are bonded to the metal via the phosphorus and the ylidic carbon atoms. The 1,5-cyclooctadiene (COD), present in the Rh(I) precursor, remains intact in the products. The structures of1,2 and3 have been confirmed by X-ray crystallography.
Chiral Phosphine−Phosphonium Ylide Rhodium Complexes
The phosphonium methylide of (R)-BINAP acts as a novel chiral dissymmetric chelating ligand in the stable [Rh(cod)(BINAPCH2)]+ complex. A rationale for the conformation of the eight-membered metallacycle derived from chiral phosphine−phosphonium ylide ligands is proposed on the basis of DFT calculations on a model complex.
Politics of Judicial Independence and Judicial Accountability in Czechia: Bargaining in the Shadow of the Law between Court Presidents and the Ministry of Justice
Judicial independence – Judicial accountability – Court presidents – Judicial politics – Separation of powers – Court administration – Judicial councils – Selection of judges – Czechia – Central Europe