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Abstract This thesis comprises four chapters: Chapter 1 includes a comprehensive literature survey concerning the previous work on ide complexes. This survey clarified several points; (i) Since the azido group is able to rdinate via different modes, the factors that govern these modes of bonding are still not 1(ully understood. (ii) Azido complexes of many 3d transition elements have not yet been ’reported. (Hi) The correlation of X-ray data and infrared vibrations with both magnetism and ’mode of bonding of the various azide groups needs a lot of work. (iv) In addition to these points the transition metal complexes of pyridine and picolinic acid show a broad variety of physiological effects on the activity functions of both animal and plant organisms. Because of these points we selected Cr(lll) as centrsal ion to be studied in an azido complex with pyridine, and Mn(II), Co(lII) together with Cu(lI) to be studied with picolinic acid as an organic ligand and azide, thiocyanate or chloride in order to compare the different characters of such complexes. Chapter 2 deals with the experimental work. We isolated the following complexes: mer-Cr(pyMN3)3 1, NaCr(py)iN3)4 2, KCr(py)iN3)4 3, RbCr(py)iN3)4 4, Mn(pic)(N3)(HzO) 5, I Mn(H-pic)(pic)CIJ2 6, Cu(pic)CI7, [Cu(pic)(SCN)(H20)zJ.2H208, and I Na2Co(pic)2(N3)2(H20)6HCo(pich(N3)2].2H20 9. The methods of preparation of these complexes and of KN3 and RbN3 are described. The instruments used for the physical measurements and the. computer programs used for the theoretical calculations are also described. Chapter 3 is concerned with the theoretical bases of the calculations: (i) The calculations of the unit cell parameters from the different X-ray diffraction methods. The solution of the phase problems and corrections of the intensity of the reflected X-ray beams are given. (ii) Introduction of the crystal field model and the calculations of the relevant energies for the CrOll) ion in the free ion state and in octahedral field are described. Chapter 4 include the results and discussion of the various measurements and calculations. This chapter is divided into several parts. |