Date of Award
12-1976
Document Type
Dissertation
Degree Name
Doctor of Philosophy (PhD)
Legacy Department
Chemistry
First Advisor
John F Gelran
Second Advisor
H. Saith Spencer
Third Advisor
Farrell B. Brown
Abstract
The unsymmetrical, heterocyclic, secondary amines, 2-pyridyl-2'-pyrimidylamine (HPPA), 2-pyridyl-2'-thiazolylamine (HPTA), 2-pyridyl-2'-(4 -methylthiazolyl)amine (HMPTA), and 2-(6-methylpyridyl)-2 ' -(4-methylthiazolyl) amine (HDMPTA), have been prepared and characterized by analysis and mass spectroscopy. All four amines act as bidentates in forming coordination compounds having the general formula, Cu(HL)2(Cl04)2, where the HL represents the neutral amine. Spectral and magnetic evidence indicates a pseudotetrahedral ligand field geometry in the solid state for all four compounds except the unstable HDMPTA complex. Upon solution the HPPA and HPTA compounds add two solvent molecules to the Cu2+ coordination sphere probably in a trans fashion; the HMPTA and HDMPTA complexes react irreversibly by an electrontransfer process. Cu(HPTA)2(ClO4)2 and Cu(HMPTA)2(ClO4)2 have each been deprotonated to give neutral compounds with the general formula, CuL 2, where L is the ligand anion. The solvent independent spectra of each complex are characteristic of pseudotetrahedral ligand fields. Hg(HPPA)2(ClO4)2, Hg(PPA)2, Pd(HPPA)2(ClO4)2, Pd(HPTA)2(CLO4)2, Pd(HMPTA)2(ClO4)2*2H2O, Pd(MPTA)2*H2O, Pd(HDMPTA)2(ClO4)2, and Pd(DMPTA)2*H20 have also been prepared and characterized. All of these compounds are diamagnetic. Attempts to prepare the 2:1 (amine:metal), HPTA, HMPTA, and HDMPTA Hg 2+ comp l exes resulted in polymeric compounds whose analyses indicated a ligand to metal ratio of 1.
Recommended Citation
Gouge, Edward Max, "Bis(Bidentate) Transition Metal Complexes of Unsymmetrical, Heterocyclic, Secondary Amines" (1976). Archived Dissertations. 14.
https://open.clemson.edu/arv_dissertations/14