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|Title: ||An Exploration of the Structural, Electronic, and Anion Binding Properties of 2-Indolylphosphines|
|Authors: ||Yu, Joanne|
|Advisor: ||Farrar, David|
|Keywords: ||X-ray crystallography|
|Issue Date: ||26-Feb-2009|
|Abstract: ||2-Indolylphosphines are unique ligands which have the capability for further phosphine modification by introducing substituents on an indolyl nitrogen centre. Substituents can vary in electronics, sterics, chirality, and can contain amino or phosphino groups which result in a multidentate (P,N)- or (P,P)-2-indolylphosphine.
X-ray crystallography was used predominantly to examine and analyze the structural features of 2-indolyphosphines and their metal complexes. While the cone angles could not be determined crystallographically, the sum of the <CPC bond angles provided some information on the steric crowding around a phosphorus atom in selected 2-indolylphosphines.
The symmetric tris-2-(3-methylindolyl)phosphine demonstrated anion binding ability through its three indolyl NH sites. Titrations to a series of selected anions were carried out; it was determined that tris-2-(3-methylindolyl)phosphine binds to these selected anions in a 1 : 1 receptor to anion binding ratio. Crystal structures of the fluoride and acetate complexes confirm the binding stoichiometry, and demonstrate the cooperative interaction of all three indolyl NH sites with the anion guest. Synthetic routes to new anion receptors with three or two indolyl NH donors were explored. The second type yielded a molecular cleft that was used in anion binding studies.
The net basicity of a 2-indolylphosphine was determined through formation of a Ni(CO)3L complex. Net basicity can be tuned by changing the substituents on phosphorus or on an indolyl nitrogen centre. The [Cu(tris-2-(3-methylindolyl)phosphine)(phenanthroline)]BF4 complex is a discrete ion pair complex, exhibiting coordination chemistry at the phosphorus centre of the phosphine, while simultaneously hydrogen bonding through the indolyl NH sites to the BF4- anion. Complexes of the type [Pd(L)Cl(mu-Cl)]2 were analyzed by crystallography and the effect of net basicity on Pd-P bond length examined.
The solid-state structures of (P,N)- and (P,P)-2-indolylphosphines were evaluated. In general, the sum of the <CPC bond angles increased from the parent unfunctionalized 2-indolylphosphine. The metal complexes of (P,N)- and (P,P)-2-indolylphosphines were assessed by crystallography to find possible trends of trans-influence.
Lastly, a tetradentate tripodal ligand was synthesized by furnishing diphenylphosphino substituents on the indolyl nitrogen centres of tris-2-(3-methylindolyl)phosphine. The coordination of the tetradentate tripodal ligand to Pt(II) or Rh(I) resulted in five-coordinate trigonal bipyramidal complexes.|
|Appears in Collections:||Doctoral|
Department of Chemistry - Doctoral theses
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