Formal Insertion Reactions Of Stannylenes And Germylenes Into Phosphorus-Halogen Bonds: A Structural And Mechanistic Investigation

<p>Insertion reactions of Group 14 carbenoids, divalent species of the form (R₂N)₂M (M = Ge or Sn) into the P-halogen bond of halophosphines have been known for some time. However, very few examples have been reported and no evidence has been presented regarding the mechanism by which these reactions take place. Comparatively, insertion of the same or analogous carbenoid species into C-halogen bonds have been </p> <p>thoroughly explored for scope and application, and the mechanism has been investigated multiple times. </p> <p> In this dissertation, numerous new examples of insertion products of Group 14 carbenoids into P-halogen bonds are presented. This array of products has been characterized by <super>31</super>P{<super>1</super>H} and <super>1</super>H NMR spectroscopy and single-crystal X-ray diffraction analysis. In addition, purity of the obtained compounds has been confirmed by elemental analyses. </p> <p> In concert with a diverse group of products, kinetic experiments were employed to examine the possible mechanistic pathways. All reasonable pathways for these reactions are discussed, analyzed and compared. Additionally, as most tin-containing insertion products are unstable, the likely mechanisms for their decomposition are discussed in detail.</p>

Name thesis:degree_name

Doctor of Philosophy (PhD)

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Year

2012

Author dc:creator

• West, Joseph Kent

Contributors dc:contributor

• Lothar Stahl

• chlorophosphines, Ge-P bond, germylenes, insertion, Sn-P bond, stannylenes

Repository record dc:identifier

https://commons.und.edu/theses/1327

OAI identifier oai:identifier

oai:commons.und.edu:theses-2328