Liu, Sung-Ying; (1997) Steric effects in lanthanide pyrazolylborate chemistry. Doctoral thesis (Ph.D.), University College London.

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Abstract

This thesis is concerned with the exploration of steric effects in the chemistry of trivalent lanthanides with the hydro-tris(3,5-dimethylpyrazolyl)borate ligand (TpMe,Me). Chapter One consists of a general introduction to the lanthanide elements and their compounds, together with a discussion of the poly(pyrazolyl)borate ligands in general. In Chapter Two, the preparation of a series of complexes Ln(TpMe,Me)2(OTf) is reported together with their acetonitrile adducts. The crystal structures of [La(TpMe,Me)2(MeCN)(OTf)](MeCN) and [Nd(TpMe,Me)2(MeCN)2](OTf) are discussed. In addition, the preparation of [La(TpMe,Me)2(NO3)] and its crystal structure is reported. In Chapter Three, the substitution of the triflate anion of Ln(TpMe,Me)2(OTf) by small unidentate anionic and potentially multidentate ligands is reported. Attempts to prepare Ln(TpMe,Me)3 complexes were found to yield [Ln(TpMe,Me)2(dmpz)] and 3,5- dimethylpyrazabole. The crystal structure of the latter is discussed. The crystal structure of a hydrolysis product of [La(TpMe,Me)2(dmpz)], [Ln(TpMe,Me)(dmpz)2BH((μ-O)]2 is reported and discussed. In Chapter Four, the preparation and crystal structure of [Sm(TpMe,Me)2Cl] is reported together with attempts to make the corresponding bromide. The preparation of chalcogenolate and transition metal carbonylate derivatives containing Sm(TpMe,Me)2 moiety by the substitution of chloride in [Sm(TpMe,Me)2Cl] or by the oxidation of divalent [Sm(TpMe,Me)2] are also reported, together with a discussion of the crystal structures of [Sm(TpMe,Me)2(OPht-Bu)], [Sm(TpMe,Me)2](Te3Ph2) and [(TpMe,Me)2Sm(μ-CO)Mo(CO)2(MeCp)]. Chapter Five reports the experimental details and characterizing data.

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