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Title page for ETD etd-06212017-095136


Type of Document Dissertation
Author Boyde, Nicholas Charles
Author's Email Address nicholas.c.boyde@vanderbilt.edu
URN etd-06212017-095136
Title Synthesis and reactions of sterically encumbered inorganic and organometallic complexes
Degree PhD
Department Chemistry
Advisory Committee
Advisor Name Title
Timothy P. Hanusa Committee Chair
Charles M. Lukehart Committee Member
David W. Wright Committee Member
James E. Wittig Committee Member
Keywords
  • bulky ligands
  • Inorganic synthesis
  • mechanochemistry
Date of Defense 2017-06-19
Availability restrictsix
Abstract
Preparation of various small inorganic and organometallic complexes was completed to determine their structural characteristics and potential applications. These compounds incorporated main group and early transition metals with a range of ligands, including cyclopentadienyl rings, halides, alkoxides, amides, and allyls. Traditional solvent methods as well as solvent-free mechanochemical methods were used in the syntheses. Ball milling the dry reagents often yielded product distributions that were similar to those from reactions conducted in hexanes, and different from reactions performed in tetrahydrofuran (THF).

The group 15 amide P[N(SiMe3)2]3 was prepared for the first time, and its structure, along with that of its heavier congeners (M = As–Bi), was analyzed both with X-ray crystallography and with density functional theory (DFT) methods. Structural distortions in the complexes that were evidently the result of simple steric crowding mimicked those that have been attributed to agostic interactions in lanthanide compounds. Group 4 mixed ligand species, in the form of CpmMXn(OR)4-(m+n) (X = Cl, Br; R = Me, Et, iPr, tBu) complexes, were prepared by either solvent-based or mechanochemical means. Adjustments in the molar ratios of reagents were largely reflected in the compositions of the products. The compounds containing tert-butoxide ligands displayed wide M–O–C angles, which were confirmed with DFT methods to be the result of metal-alkoxide π-bonding. Attempts to produce the unsolvated bis(allyl)beryllium compound [1,3-(SiMe3)2C3H3]2Be resulted instead in the generation of the potassium tris(allyl)beryllate, K[Be{1,3-(SiMe3)2C3H3}3]; it is isostructural with previously described zinc and tin analogs. The unsolvated [1,3-(SiMe3)2C3H3]2Be may be too coordinately unsaturated to be readily isolated.

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