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
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