Date of Award
Chemistry and Biochemistry
Charles L. B. Macdonald
Coordination, Inorganic Chemistry, Lewis Acids, Main Group Chemistry, Pincer Ligands, Triels, Tetrels, Pnictogens
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2,6-bis(benzimidazol-2-yl)pyridine derivative (G-BZIMPY, G = NBn, N(3,5-CF3)Bn, N-allyl and O) have been used as pincer ligands to coordinate and isolate various group 13-15 complexes. For Group 13, treatment of G-BZIMPY with two equivalents of GaCl3 results in the self-ionization products [G-BZIMPYGaCl2][GaCl4]. This Ga(III) complex can be reduced to a Ga(I) centre using K2[Fe(CO)4] as a reducing agent to result in the Ga(I) complex [(NBn-BZIMPY)(Cl)Ga–Fe(CO)4] (Chapter 2).
Group 14 complexes of G-BZIMPY have been synthesized in a similar fashion through the self-ionization reactions of G-BZIMPY with two equivalents of MCl2 (M = Ge, Sn) to yield [G-BZIMPYMCl][MCl3]. Attempts to reduce these complexes into the M(0) centre were not successful. Other reactivities and UV-vis studies are detailed in this dissertation (Chapter 3). Comparison of group 13 and 14 complexes of G-BZIMPY to complexes of the structurally similar bis(imino)pyridine (DIMPY) are studied and reveal G-BZIMPY as a stronger donor than DIMPY for group 13 coordination. For group 15 elements, treatment of PnCl3 (Pn = P, As, Sb) with G-BZIMPY does not yield any reactivity, however, the addition of TMS-OTf (Trimethylsilyl trifluoromethanesulfonate) results in the isolation of [G-BZIMPYPnCl][OTf]2 (Chapter 4).
In-addition, a tetradentate ligand tris((1-ethyl-benzoimidazol-2-yl)methyl)amine (BIMEt3) has been investigated. A series of cationic complexes involving a pnictogen(III) (Pn = P, As, Sb) centre coordinated to BIMEt3 have been synthesized and comprehensively characterized. Oxidation of [P(BIMEt3)]3+ with XeF2 provides access to [PF2(BIMEt3)]3+ representing the first structurally characterized example of a phosphorus(V) centred trication (Chapter 5). Attempts to synthesize an anionic carbon(0) are detailed in chapter 6. Although obtaining an anionic carbon(0) was not successful, it lead to a series of interesting compounds and results. Compounds containing carbon centre behave differently than their heavier group-14 analogues of the same bidentate anionic bisphosphine ligand.
Swidan, Ala'aeddeen, "Synthesis, Characterization, and Reactivity of Chelating Ligand Complexes of Group 13-15 Elements" (2019). Electronic Theses and Dissertations. 7761.