Syntheses and spectral properties of two complexes of isonitrosoacetylacetone acetone-N-arylimine imine and crystal structure of PdCl(C6H5-IAI) (C6H5NH2)

Two complexes of isonitrosoacetylacetone-N-arylimine, PdCl(C6H5-IAI) (C6H5N H2)(1) and PdCl(p-CH3C6H4-IAI) (p-CH3C6H4NH2) (2), were synthesized and cha racterized by IR and Raman spectroscopy. Complex 1 crystallizes in orthorho mbic system, space group Pca2(1), with parameters a = 1. 858 7(4) nm, b = 0 . 938 0(2) nmr c = 2. 123 1(4) nm, V = 3. 702(1) nm(3), D-c = 1. 512 g/cm(3 ), Z = 8, F(000)=1 760, mu = 1. 160 mm(-1). The final R-1 value is 0. 027 1 for 3 592 observed reflections with I greater than or equal to 2 sigma(I). The Pd(II) ion has a distorted square-planar PdN3Cl coordination composed of imino-nitrogen and oximo-nitrogen from the Schiff base ligand, amino-nit rogen from aniline and chlorine anion. The oxime group of the Schiff base l igand is coordinated to the Pd(II) through its oximo-nitrogen atom, but not its oximo-oxygen atom. The v(C=O) and v(C=N) bands display a shift to lowe r frequencies and v(N-O) bands to higher frequencies in IR and Raman spectr a. There ate pi-pi* transition and d-pi* charge-transfer transition in elec tronic spectra.