Date of Award

1984

Degree Type

Dissertation

Degree Name

Ph.D.

Department

Chemistry and Biochemistry

Keywords

Chemistry, Inorganic.

Rights

CC BY-NC-ND 4.0

Abstract

Nine adducts of the type Me(,n)AsH(,3-n).BX(,3) and several mixed halide derivatives of the general formulae Me(,n)AsH(,3-n).BX(,2)Y and Me(,n)AsH(,3-n).BXYZ (n = 1,2,3; X,Y,Z = Cl,Br,I) have been prepared. Their i.r. and Raman spectra have been recorded and normal coordinate analysis utilized as a confirmation of the vibrational assignments of MeAsH(,2) and Me(,2)AsH adducts. The crystal structures of the three Me(,3)As.BX(,3)(x = Cl,Br,I) adducts have been determined and a comparison drawn with many conclusions based on the vibrational analysis. The molecules are shown to possess an As-B coordinate bond and to have C(,3v) symmetry with staggered conformation. The ('1)H and ('11)B chemical shifts have been recorded and used to indicate relative acidity and basicity of the acceptor and donor species. The synthesis and characterization of some selenium ligands of the type Me(,3)MCH(,2)SeR where M = Si,Ge,Sn; R = Me,Ph, are reported. I.r., Raman, ('1)H and ('13)C n.m.r. spectra are employed to characterize these ligands. Selected reactions of these compounds with Na(,2)PdCl(,4), and K(,2)PtCl(,4) have produced a series of new coloured Pd(II) and Pt(II) complexes. The crystal structure of dichlorobis (methyl trimethylsilylmethyl selenide) palladium (II), (Me(,3)SiCH(,2)SeMe)(,2)PdCl(,2), shows the molecule to be square planar with the ligands in the trans arrangement at palladium bonded by selenium. Ab initio molecular orbital calculations were performed on axial-, equatorial-, and square pyramidal SiF(,4).NH(,3) and also on cis- and trans-SiF(,4).2NH(,3) complexes. The electronic structures of these five isomers were determined and their relative stabilities discussed. Source: Dissertation Abstracts International, Volume: 45-04, Section: B, page: 1186. Thesis (Ph.D.)--University of Windsor (Canada), 1984.

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