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Theses Doctoral

Synthetic and Structural Investigations of Main Group and Transition Metal Compounds Supported by a Multidentate [N3C] Donor Ligand

Hammond, Matthew James

Recently, the Parkin group has synthesized tris[(1-isopropylbenzimidazol-2-yl)dimethylsilyl]methane, [Tismᴾʳⁱᴮᵉⁿᶻ]H, a bulky tetradentate tripodal ligand, which upon deprotonation can coordinate to metal centers via three nitrogen donor atoms and a carbon bridgehead to form metal atrane compounds. The [Tismᴾʳⁱᴮᵉⁿᶻ] ligand has been previously shown to stabilize metal hydride complexes, for example [Tismᴾʳⁱᴮᵉⁿᶻ]MgH [Tismᴾʳⁱᴮᵉⁿᶻ]ZnH. However, no attempts had been previously made to employ this ligand to stabilize heavier Group 12 analogues of these complexes, namely the cadmium and mercury hydride derivatives. In addition, all [Tismᴾʳⁱᴮᵉⁿᶻ] complexes previously reported have employed metals in the first or second oxidation states. In this work, an investigation is undertaken to use the [Tismᴾʳⁱᴮᵉⁿᶻ] ligand to stabilize rare examples of cadmium and mercury hydrides, as well as survey how this ligand binds to Group 13 and transition metals in a variety of oxidation states.

In Chapter 1, a series of [Tismᴾʳⁱᴮᵉⁿᶻ] cadmium complexes are reported, including the novel cadmium hydride species [Tismᴾʳᴮᵉⁿᶻ]CdH, which is only the third terminal cadmium hydride species to be structurally characterized by X-ray diffraction. The reactivity of this complex has been probed, revealing the first detailed report of reactivity for a Cd-H bond, as well as the first comparison in relative reactivity between an analogous Cd-H and Zn-H bond. This reactivity of [Tismᴾʳⁱᴮᵉⁿᶻ]CdH includes the ability to insert CO₂ and CS₂, and the resulting cadmium formate and dithioformate complexes have been characterized and discussed, with the latter being the first structurally characterized example of a cadmium dithioformate complex. In addition, [Tismᴾʳⁱᴮᵉⁿᶻ]CdH can undergo hydride extraction to yield the ion pair {[Tismᴾʳⁱᴮᵉⁿᶻ]Cd}[HB(C6F5)₃], a rare example of trigonal monopyramidal cadmium complex. Finally, [Tismᴾʳⁱᴮᵉⁿᶻ]CdMe was synthesized, revealing a different coordination mode of the [Tismᴾʳⁱᴮᵉⁿᶻ] ligand than in the analogous [Tismᴾʳⁱᴮᵉⁿᶻ]ZnMe.

In Chapter 2, a series of [Tismᴾʳⁱᴮᵉⁿᶻ] mercury complexes are reported and compared with their cadmium analogues. This comparison revealed several notable differences between [Tismᴾʳⁱᴮᵉⁿᶻ] mercury and cadmium complexes, most notably that the M-O-Si bond angle in [Tismᴾʳⁱᴮᵉⁿᶻ]HgOSiPh₃ is bent, as opposed to the linear [Tismᴾʳⁱᴮᵉⁿᶻ]CdOPh₃ derivative. The synthesis and characterization of [Tismᴾʳⁱᴮᵉⁿᶻ]HgH, the first mercury hydride complex to be structurally characterized by X-ray diffraction, is also reported. This complex has been crystallized in both the κ⁴ and κ³-coordination mode of the [Tismᴾʳⁱᴮᵉⁿᶻ] ligand, representing the first example of a [Tismᴾʳⁱᴮᵉⁿᶻ] compound to be structurally characterized in two coordination modes.

In Chapter 3, the synthesis of Group 13 and transition metal [Tismᴾʳⁱᴮᵉⁿᶻ] complexes are reported. These compounds include the first examples of [Tismᴾʳⁱᴮᵉⁿᶻ]M(III) complexes, which reveal that trivalent Group 13 [Tismᴾʳⁱᴮᵉⁿᶻ]M halide compounds form charged ion pairs, whereas trivalent transition metal chloride compounds form six-coordinate octahedral complexes. The investigation into Group 13 [Tismᴾʳᴮᵉⁿᶻ] complexes also led to the structural characterization of [Tismᴾʳⁱᴮᵉⁿᶻ]In→InI₃, the first example of a [Tismᴾʳⁱᴮᵉⁿᶻ] compound with a metal-metal bond. A series of [Tismᴾʳⁱᴮᵉⁿᶻ]MCl (M = Mn, Fe, Co, Cu) complexes are reported and their metrical data compared, along with an investigation into the reactivity of [Tismᴾʳⁱᴮᵉⁿᶻ]NiBr, which led to spectroscopic evidence for a [Tismᴾʳⁱᴮᵉⁿᶻ]NiH complex. Finally, the gold complex [κ1-Tismᴾʳⁱᴮᵉⁿᶻ]AuPPh₃ is reported, which adopts a novel κ1-coordination of the [Tismᴾʳⁱᴮᵉⁿᶻ] ligand.

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More About This Work

Academic Units
Chemistry
Thesis Advisors
Parkin, Gerard
Degree
Ph.D., Columbia University
Published Here
August 4, 2021