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

Mouat, Aidan Richard (2009)

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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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