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Transition Metal Chelates with Schiff Bases Derived from Salicylaldehyde

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Transition Metal Chelates with Schiff Bases Derived from Salicylaldehyde I TRANSITION METAT CHETATES \ryITH SCHIFF BASES DERIVED FROM SATICYTATDEHYDE AND DIAMINO ETHANE ALVIN PAUL SUMMERTON, a.sc. UNIVERSITY OF ADELAIDE, DEPARTMENT OF PHYSICAL AND INORGANIC CHEMISTRY November 1978 1tu¡artol q''-'t tÇ14 Pl.l CONTENTS Page SUMII{ARY STATEMENT ACKNOhTLEDGEMENTS ABBREVIATIONS CHAPTER 1: Introduction t PART Ï CHAPTER 2: Preparation and characterization of salen complexes of iron (III) 6 CHAPTER 3: Solut.ion studies 30 CHAPTER 4: Moessbauer .spectra 57 PART II CHAPTER 5: Preparation, characterization and solid state properties 84 CHAPTER 6: Solution studies 115 CHAPTER 7: Crystal structure of Fe (saen) 2C1-.H2O 143 APPENDTX I: Computer Programs APPENDÏX II: Structure Factor Tables APPENDTX III: Publication BIBLTOGRAPHY SUM¡{ARY The following study of transition metal complexes with Schiff base ligands comprises two related studies. PART I Complexes of the quadridentate ligand, sa1en. A number of complexes of general formula Fe(III)salenX, where X = Cl, Br, I, NO3, N3, NCS and C6H5COO, have been pre- pared. Of these species, two (X = NO3 and N3) have not been previously reported and only one (X = Cl) has been intensively studied. In addition, two novel octahedral complex salts KlFesalen(CN)21 and Fe(saen) 2C1-.H2O, which involve a low spin central metal ion, have been obtained. The salt Fe(saen) 2CI. H2O has several unusual properties which have been examined in Part II of this thesis. This j-nvestigation of the salen complexes has involved: (1) confirmation of structure by microanalysis, i.r. spectra and magnetism; (2\ a sÈudy of the u.v.-visible solution spectra; (3) deterinination of the Moessbauer spect.ral parameters. The solution spectra indicated that the species were in- volved in dissociative equilibria which were utilized to estimate the relative stability of the covalent bond between the metal and the anionic ligand occupying the fifth coordination position. fn contrast to previous studies, where a correlation between magnetic properties and the Moessbauer data was indicated, the results of this work suggested that the magnitude of the quad- rupole splitting may be related to the nature of the Fe-X bond. PART TI Comple xes of the trldentatê liqand , saen. cationic salts of general formura M(rrr) (saen) 2x.nT)o, where X = CI, Br, I, NO3, NCSrC1O4, BF4 and. pF6r n = 0 or l, have been prepared and confirmed. by microanarysis for M = cr, Fe and Co. The properties of these salts have been studied. in the sorid state utitiri\g a variety of techniques incruding i.r spectra, x-ray powder diffraction, magnetic susceptibility and dehydration in vacuo. The characteristic i.r. spectra obtained allowed classification of the sarts into one of three general spectral types. This classification was found to be dependent on the nature of both the metal and anion in addition to the presence or absence of water of hydration The chloride salts of aIr three comprex metar cations v¡ere found to be isostructural monohydrates of particurar inter- est. The water morecule appeared to be unusual in that it: (1) produced two sharp absorptions in the O-H stretching region of the i.r. spectrum; (2) stabilized the low spin state of Fe(III) in Fe(saen) zCI. Hzo. The solution properties of the salts \^rere studied via n.m-r. and u.v.-visible spectra, conductance and magnetic susceptibility measurenrents. In contrast to the resul-ts obtained in water and alcohol, association of the chloride sal-ts was ob- served in the aprotic solvent DMSO, wíth the evidence supporting the conclusion that the water morecule also remained bound. rn order to rationalize the behaviour of the water more- cule, the molecular structure of Fe(saen) 2Cl-.H2O was determined by the single crystal x-ray diffraction technique. The water molecule was found to be strongly bound into the crystal lattice via unusual, specific hydrogen bonding interactions. These specific ínteractions involve one cation ammine hydrogen atom with the water oxygen and one water hydrogen atom with the anion. The mode of bonding of the water molecule has enabled the above- mentj-oned unusual features to be explained. STATEMENT This thesis contains no materiat which has been accepted for the award of any other degree or diploma in any university, and to the best of my knowled.ge and belief, contains no mater- ial previously published or written by another personr gxc€pt where due r,eference is made in the text of the thesis. A. P. SUMMERTON ACKNOWLEDGEMENTS My sincerest thanks are extended to all who have been in- volved with my research project friends, colleagues and students at both the S.A. Institute of Technotogy and the University of Ade1aide. I am grateful to prof. R.V. Cu1ver of S.A.I.T. and Prof. D.O. Jordan of the University for making available to me the facilities to undertake this worki to Dr. Mike Snow and Mr. John Vrlestphalen for assistance with the crystat structure, and to Mrs. Trish McMurtrie for the typing of this thesís. The expertise, interest and friendship of Mr. Keith Johnson of S.A.I.T. has been appreciated immensely. The guidance, patience, consideration and advice f have re- ceived from my supervisor, Dr. Alex Diamantis, over a number of years, has proved of inestimable value in completing this research. Finally, I am indebted to my parentsr my wife Kathryn and daughters, Lynda and Kerry, to whom I wish to dedicate this work. ABBREVIATIONS The following abbreviations have been used in the text of this thesis: acac Acetylacetonate C6H5COO Benzoato DMF Dimethyl formamide DMSO Dimethylsulphoxide Et'OH Ethanol en 1,2 diaminoethane (ethylenediamine ) MeOH Methanol ophen 2 aminoaniline (o-phenylenediamine ) pn L12 diaminopropane (propylenedi amine) sal salicylaldehydato Structures of the Schiff base ligands involved in this study: salen N N \ I CH z-H zc o- saen \ /N"z CH -H c 2 2 salpn o- -o T H-I{ c 2 H 3 saloph-en -o =\J I CHAPTER I 1.1 TNTRODUCTION From an historical viewpoint, chemistry received recog- nition as a scientific discipti-ne in its own ríght as recently as L789, with the establishment of the first Chair in chemistry(1). Prior to this, it rnras merery considered to be a branch of Medical science. The profound infl-uence of the 'biologicar biasr in scientific thought is readily reflected in the controversy surrounding the 'vitar force' theory, which many scientists regard as having significantly retarded the advancement of organic chemistry during the early nineteenth c"rrtrrry(2). An indication of the animosity generated by this controversy is provided by Berzerius, whor orr being informed of wohrerrs urea synthesis, is reported Èo have stated that 'whosoever started on the path of, immortal fame with urine was (3). bound to end in i¡' chemistry has rapidly developed d.uring the ensuing period, with the inevitabre accumuration of a vast mass of knowledge. rt is hardry surprising that sub-division into major areas, such as Analytical, rnorganic, Physicat, organic and Biochem- istry, has occurred in an effort to quantify this knowledge. Such areas have become effectively isolated tiisciplines today, and increasing speciatization in narrower and narrower fields appears the norm for postgraduate research. It is interesting to noÈe an apparent reversal in this trend where emphasis is placed on the interaction between supposedly isolated disciprines. As a particurar example, the 2 rapidry developing field of Bio-inorganic chemistry overlaps significantly into areas traditionalry associated with Bio- chemistry and Biology(4). rn this field, the especiat expert- ise of the coordination chemist is applied to specific problems, of major importance to the 'rife sciences' , such as the chem- istry of the important naturalry occurring metarloprotein= (4). A particurarly useful approach utirizes ,model compoundsr, whereby, through the invention, synthesis and.detailed. study of suitable simpre systems, some insight into the workings of the natural system may be achieved(4). A large number of the model systems involve the complexes rfamily' of a of ligands collectively referred to as 'schiff bäses'. such ligands contain the azomethine group (-Rc=N-), and one class of such compounds which has been intensively studied involves the NrN'-ethyrene bis (saricylideneimine) dianion, traditionally abbreviated as sa1en. cobart comprexes of Èhis liganit provide a typicar iIl-ustration of the appric- ation of such compounds as biorogicar models. co(rr)saten (5) (a) is able to absorb oxygen reversibty , and 'be (6) (b) may reduced to (co (r) saren) - , which reacts with arkyl halides to form complexes formulated as Rco(rrr)salen. The alkyl group, R, is directry bonded to the cobalt through the carbon .to*(7). similar reactions have been observed with a naturarly occurring system involving a coenzyme of vitamin (t). "r, Arthough schiff base complexes have proved of signifi- cance in the understanding of biological systems, Èhe chemistry of such compounds is of considerable interest in its own right 3 and has occupied a central role in the development of modern coordination chemistry(9). of all the complexes studied, those with salicylaldimine ligands, and in particular salen, have received the most attentiorr(9). rn fact a recent review, devoted solely to the c.ompounds of sa1en, cites 155 major references covering a six year period(10). No doubt this is due, in part, to thè fact that salen complexes have been obtaified htith many metals, including the majority of the trans- ition elemenÈs. However, a significant factor must be the diversity in the chemical behaviour of these compounds, as illustrated. in the review article by Hobday and Smith(10). 1.2 RESEARCH PROGRAM - Aim and Rationale The primary aim of this research study is the deter- mination of the lvloessbauer parameters for a series of iron(III) complexes and the elucidation of the correlation, if ârry, between these and other information which may be related to the bonding of ligands A convenient.
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