Rhodium complexes with diacetyl monoxime ligands ; crystal structure of [Rhcis-(C4H6NO)2cis-(PPh3) 2]ClO4·CHCl3

Article abstract of DOI:10.1016/0277-5387(96)00252-5

The reaction of RhCl₃ · 3H₂O with Hdamo and PPh₃ (Hdamo = diacetyl monoxime = C₄H₇NO), both in the absence (1) and in the presence of HClO₄ (2) afforded the complex Rh(damo)(PPh₃)₂Cl₂. The reaction of the acidic water/ethanolic solution of [Rh(H₂O)₆]³⁺ with Hdamo and PPh₃ (3) gave the mixture of the isomers of the compound [Rh(damo)₂(PPh₃)₂]ClO₄ (3B and 3B). A similar mixture of isomers was formed when [Rh(H₂O)₆]³⁺ reacted with H₂dopn (H₂dopn = 3,9-dimethyl-4,8-diazaundeca-3,8-diene-2, 10-dione dioxime) and PPh₃ (4). Two isomers (4A = 3B) and [Rhcis-(damo)₂cis-(PPh₃)]ClO₄·CHCl ₃ (4B) have been isolated. All the compounds were characterized by elemental analysis NMR and IR spectroscopy. Single-crystal X-ray diffraction studies were carried out on the complex 4B. In this compound the coordination environment around rhodium(III) is pseudooctahedral composed of two cis-oxime nitrogen atoms [av. Rh - N = 2.031(3) A], two trans-oxime oxygen atoms [av. Rh - 0 = 2.026(2) A] and two cis-phosphine phosphorus atoms [av. Rh - P = 2.403(1) A]. Copyright