The reaction of [RhCl2(HPhL)(PhL)] with MII(ClO4)2.6H2O in presence of alkali has furnished trinuclear [RhCl2(PhL)2]2M(H2O)$_2.$H2O (HPhL is phenylazobenzaldoxime; M = Mn, Co, Ni). A similar reaction with MI(PPh3)2NO3 yielded binuclear [RhCl2(PhL)2]M(PPh3)2 (M = Cu, Ag). In these molecules the oximato group acts as a bridge between RhIII (bonded at N) and MII or MI (bonded at O). In structurally characterized [RhIIICl2(PhL)2]2Mn(H2O)2.H2O the centrosymmetric distorted octahedral MnO6 coordination sphere is spanned by four oximato oxygen atoms and two water molecules lying in trans position. In the lattice the neighbouring molecules are held together by H2O$\cdots$H2O$\cdots$H2O hydrogen bonds generating infinite zigzag chains. The manganese atoms lie parallel to the C-axis, the shortest Mn…Mn distance being 7.992 Å. Magnetic exchange interactions if any are small as seen in room temperature magnetic moments. The manganese system displays a strong EPR signal near 𝑔 = 2.00. In the complex [RhCl2(PhL)2]Cu(PPh3)2 the copper atom is coordinated to two oximato oxygen atoms and the two phosphorus atoms in a distorted tetrahedral geometry. The softness of the phosphine ligand is believed to sustain the stable coordination of hard oximato oxygen to soft CuI. The coordination sphere of the RhIII atom in both the complexes is uniformly trans-RhN4Cl2.
Volume 134, 2022
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