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Reactions of small molecules facilitated by metal-acceptor interactions

Citation

Suess, Daniel Leif Migdow (2013) Reactions of small molecules facilitated by metal-acceptor interactions. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechTHESIS:05302013-182601874

Abstract

The role of metal-acceptor interactions arising from M–BR3 and M–PR3 bonding is discussed with respect to reactions between first-row transition metals and N2, H2, and CO. Thermally robust, S = 1/2 (TPB)Co(H2) and (TPB)Co(N2) complexes (TPB = tris(2- (diisopropylphosphino)phenyl)borane) are described and the energetics of N2 and H2 binding are measured. The H2 and N2 ligands are bound more weakly in the (TPB)Co complexes than in related (SiP3)M(L) complexes (SiP3 = tris(2- (diisopropylphosphino)phenyl)silyl). Comparisons within and between these two ligand platforms allow for the factors that affect N2 (and H2) binding and activation to be delineated. The characterization and reactivity of (DPB)Fe complexes (DPB = bis(2- (diisopropylphosphino)phenyl)phenylborane) in the context of N2 functionalization and E–H bond addition (E = H, C, N, Si) are described. This platform allows for the one-pot transformation of free N2 to an Fe hydrazido(-) complex via an Fe aminoimide intermediate. The principles learned from the N2 chemistry using (DPB)Fe are applied to CO reduction on the same system. The preparation of (DPB)Fe(CO)2 is described as well as its reductive functionalization to generate an unprecedented Fe dicarbyne. The bonding in this highly covalent complex is discussed in detail. Initial studies of the reactivity of the Fe dicarbyne reveal that a CO-derived olefin is released upon hydrogenation. Alternative approaches to uncovering unusual reactivity using metal- acceptor interactions are described in Chapters 5 and 6, including initial studies on a new π-accepting tridentate diphosphinosulfinyl ligand and strategies for designing ligands that undergo site-selective metallation to generate heterobimetallic complexes.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Inorganic chemistry
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Peters, Jonas C.
Thesis Committee:
  • Bercaw, John E. (chair)
  • Reisman, Sarah E.
  • Agapie, Theodor
  • Peters, Jonas C.
Defense Date:17 May 2013
Non-Caltech Author Email:daniel.l.m.suess (AT) gmail.com
Record Number:CaltechTHESIS:05302013-182601874
Persistent URL:http://resolver.caltech.edu/CaltechTHESIS:05302013-182601874
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:7777
Collection:CaltechTHESIS
Deposited By: Daniel Suess
Deposited On:01 Dec 2014 18:57
Last Modified:12 May 2015 19:21

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