Synthesis and Characterization of the Metal Complexes of [N(o-PhNHC(O)Me3]: A Tripodal, Triamidate Ligand Platform Open Access

Mouat, Aidan Richard (2009)

Permanent URL: https://etd.library.emory.edu/concern/etds/7m01bm223?locale=en
Published

Abstract

This thesis reports the synthesis and characterization of a novel tripodal, triamidate ligand [N( o-PhNHC(O)Me)3] based on a generic [N( o-PhNCH(O)R)3] platform, where R is a series of substituents varying in both steric bulk and electron-donating or -withdrawing ability. The cobalt(II), nickel(II), and zinc(II) metal complexes K[CoN( o-PhNC(O)Me)3], K[NiN( o-PhNC(O)Me)3], and K[ZnN( o-PhNC(O)Me)3] of the R = Me ligand have also been synthesized. These complexes have been characterized using NMR, FTIR, HRMS(ESI), and UV-Vis spectroscopy. They adopt a trigonal
monopyramidal geometry which is consistent with other metal complexes of the ligand platform. Spectroscopic data indicate that the complexes are most likely forming in an alternate geometry to the anticipated C3-symmetric species, occuring either as a Cs-symmetric, mixed donor amidate binding through the O-donor of one of the ligand "arm" and the N-donor of the other two, or as a C2-symmetric dimer, the model for which has
been observed in other complexes of the ligand platform. No X-ray structures of the complexes are available at present, so this geometry remains unverified.

Table of Contents

Table of Contents

List of Figures
List of Tables

Chapter 1: Introduction------------------------------------------------------------------------ 1

Chapter 2: Experimentals------------------------------------------------------------------------11

Synthesis of [N( o-PhNO2)3]------------------------------------------------------------- 12

Synthesis of [N( o-PhNH2)3]------------------------------------------------------------- 13

Synthesis of [N( o-PhNHC(O)Me)3]---------------------------------------------------- 13

Synthesis of K[Co(N( o-PhNC(O)Me)3)]---------------------------------------------- 15

Synthesis of K[Ni(N( o-PhNC(O)Me)3)]----------------------------------------------- 15

Synthesis of K[Zn(N( o-PhNC(O)Me)3)]---------------------------------------------- 16

Chapter 3: Results and Discussion------------------------------------------------------------- 18

Structural details of [N( o-PhNHC(O)Me)3]------------------------------------------- 19

Structural details of K[Co(N( o-PhNC(O)Me)3)]------------------------------------- 22

Structural details of K[Ni(N( o-PhNC(O)Me)3)]-------------------------------------- 26

Structural details of K[Zn(N( o-PhNC(O)Me)3)]------------------------------------- 27

Characterization considerations---------------------------------------------------------28

Future directions-------------------------------------------------------------------------- 30

Appendix A. Spectroscopy of [N( o-PhNHC(O)Me)3]---------------------------------------31

1H NMR of [N( o-PhNHC(O)Me)3]---------------------------------------------------- 31

13C NMR of [N( o-PhNHC(O)Me)3]----------------------------------------------------32

FTIR of [N( o-PhNHC(O)Me)3]--------------------------------------------------------- 33

HRMS(ESI) of [N( o-PhNHC(O)Me)3]------------------------------------------------ 34

Appendix B. Spectroscopy of K [Co(N( o-PhNC(O)Me)3)]--------------------------------- 35

1H NMR of K[Co(N( o-PhNC(O)Me)3)]----------------------------------------------- 35

FTIR of K[Co(N( o-PhNC(O)Me)3)]--------------------------------------------------- 36

UV-Vis of K[Co(N( o-PhNC(O)Me)3)]-------------------------------------------------37

HRMS(ESI) of K[Co(N( o-PhNC(O)Me)3)]------------------------------------------- 38

Appendix C. Spectroscopy of K [Ni(N( o-PhNC(O)Me)3)]----------------------------------39

1H NMR of K[Ni(N( o-PhNC(O)Me)3)]----------------------------------------------- 39

FTIR of K[Ni(N( o-PhNC(O)Me)3)]---------------------------------------------------- 40

UV-Vis of K[Ni(N( o-PhNC(O)Me)3)]------------------------------------------------- 41

HRMS(ESI) of K[Ni(N( o-PhNC(O)Me)3)]------------------------------------------- 42

Appendix B. Spectroscopy of K [Zn(N( o-PhNC(O)Me)3)]--------------------------------- 43

1H NMR of K[Zn(N( o-PhNC(O)Me)3)]----------------------------------------------- 43

13C NMR of K[Zn(N( o-PhNC(O)Me)3)]---------------------------------------------- 44

FTIR of K[Zn(N( o-PhNC(O)Me)3)]--------------------------------------------------- 45

HRMS(ESI) of K[Zn(N( o-PhNC(O)Me)3)]------------------------------------------- 46

About this thesis

Rights statement
  • Permission granted by the author to include this thesis or dissertation in this repository. All rights reserved by the author. Please contact the author for information regarding the reproduction and use of this thesis or dissertation.
School
Department
Degree
Submission
Language
  • English
Research field
Keyword
Committee Chair / Thesis Advisor
Committee Members
Last modified

Primary PDF

Supplemental Files