Studies on some Metal Complexes of Dithio Ligands

The thesis deals with our studies on the synthesis and elucidation of structure of some metal complexes of dithio ligands, such as the dithiocarbamates, xanthates and 2-aminocyclopent-1-ene-1-dithiocarboxylate and its N-alkyl derivatives.2-Aminocyclopent-1-ene-1-dithiocarboxylate (ACDA) is an interesting ligand, because of its potential dual capability of bonding between the metal and the ligand. Since the earlier reports on the complexes of ACDA contain contradictory ideas on the nature of its bonding, it was thought worthwhile to undertake a detailed and systematic study of these type of complexes. As the ACDA complexes have very low solubilities in solvents like chloroform, we have used the isopropyl derivative of ACDA as the ligand. The increased solubility of these complexes have made it possible to investigate their NMR and solution electronic spectra.The complexes of this ligand have not yet been reported in the literature.We have synthesised some new mixed ligand complexes of dithiocarbamates by reacting bis(dithiocarbamato)-µ-dichloro dicopper complexes (obtained by the reaction of mixed benzoic dithiocarbamic anhydride and copper(II) chloride) with ACDA or its N-alkyl derivatives.Interactions of metal halides with the mixed anhydrides formed from benzoylchloride and xanthates have also been investigated. Novel complexes of the type, [Cu2(RXant)CI] (R=i-Bu, i-Pr, n-Bu or n-Pr)) have been isolated from the reaction of copper(II) chloride and the mixed anhydride, and these reactions appear to be like the clock reactions reported in the literature.It also deal with the characterisation of the complexes of the type [Hg(R2d t c )X] (X=Cl, Br or 1),[Cu3(R2dtc)6][Cu2Br6] and [Cu(R2dtc)Cl2](R2=Me2,Et2,Pip,Morph or Pyrr)respectively, synthesised by simple and novel routes, different from those reported earlier.

Transition metal complexes of quinoxaline based Schiff base ligands: Synthesis,characterization and catalytic activity study

Schiff base complexes of transition metal ions have played a significant role in coordination chemistry.The convenient route of synthesis and thermal stability of Schiff base complexes have contributed significantly for their possible applications in catalysis,biology,medicine and photonics.Significant variations in cataltytic activity with structure and type are observed for these complexes.The thesis deals with synthsis and characterization of transition metal complexes of quinoxaline based Schiff base ligands and their catalytic activity study.The Schiff bases synthesized in the present study are quinoxaline-2-carboxalidine-2-amino-5-methylphenol,3-hydroxyquinoxaline-2-carboxalidine-2-amino-5-methylphenol,quinoxaline-2-aminothiophenol.They provide great structural diversity during complexation.To the best of our knowledge, the transition metal complexes of quinoxaline based Schiff bases are poorly utilised in academic and industrial research.

Structural Characterization and Non-linear Optical Properties of Metal Complexes of Some Donor-Acceptor Substituted N-salicylidene-N' -aroylhydrazine Ligands

The present work deals with the complexation of Schiff bases of aroylhydrazines with various transition metal ions. The hydrazone systems selected for study have long 7I:-delocalized chain in the ligand molecule itself, which get intensified due to metal-to-ligand or ligand-to-metal charge transfer excitations upon coordination. Complexation with metal ions like copper, nickel, cobalt, manganese, iron, zinc and cadmium are tried. Various spectral techniques are employed for characterization. The structures of some complexes have been well established by single crystal X-ray diffraction studies. The nonIinaer optical studies of the ligands and complexes synthesized have been studied by hyper-Rayleigh scattering technique.The work is presented in seven chapters and the last one deals with summary and conclusion. One of the hydrazone system selected for study proved that it could give rise to polymeric metal complexes. Some of the copper, nickel, zinc and cadmium complexes showed non-linear optical activity. The NLO studies of manganese and iron showed negative result, may be due to the inversion centre of symmetry within the molecular lattice.

Self-assembled Transition Metal Coordination Frameworks of Carbohydrazone and Thiocarbohydrazone Ligands: Structural, Spectral, Magnetic and Anticancer Properties

Chemistry occupies a unique middle position in the scientific arena, between physics and mathematics on the one side and biology, ecology, sociology and economics on the other [1]. Chemistry is the science of matter and of its transformations, and life is its highest expression [2]. According to reductionist thinking biology is reducible into chemistry, chemistry into physics, and ultimately physics into mathematics. Reductionism implies the ease of understanding one level in terms of another.The work presented this thesis comprises synthesis and characterization of suitably substituted thiocarbohydrazone and carbohydrazone ligand building blocks, self-assembled metallosupramolecular square grid complexes as well as some di/multinuclear complexes. The primary aim was the deliberate syntheses of some novel transition metal framework complexes, mainly metallosupramolecular coordination square grids by self-assembly and their physico-chemical characterization. The work presented, however, also include synthesis and characterization of four mononuclear Ni(II) complexes of two thiosemicarbazones, which we carried out as a preliminary and supporting study. Based on the present work we would like to conclude that the carbohydrazones, thiocarbohydrazones and their coordination framework complexes of transition metals are promising systems for wide application in science and technology varied from physics to biotechnology. Novel classes of materials and biologically important potential compounds open up further scope of researches and we hopefully welcome any sort of related research to make this work more valuable.

Investigations on the Structural, Spectral and Magnetic Interactions of Transition Metal Complexes of Multidentate Ligands from Di-2-pyridyl ketone and N(4)-substituted Thiosemicarbazides

The present work deals with the investigations on sthe structural spectral and magnetic interactions of transition metal complexes of multidentate ligands from D1-2-pyridyl ketone and N(4)-Substituted thiosemicarbazides.Thiosemicarbazones are thiourea derivatives with the general formula R2N— C(S)—NH—N=CR2. In the solution state, the thiosemicarbazones exhibit the thionethiol tautomerism similar to the keto-enol tautomerism, and in solution state the thiol form predominates and a deprotonation at the thiolate group in alcoholic medium enhances the coordination abilities ofthe thiosemicarbazones.The magnetochemistry of metal complexes of di-2-pyridyl ketone is a current hot subject of research, which mainly owes to the excellent structural diversity of the complexes ranging from cubanes to clusters, with promising ferromagnetic outputs.Only few efforts were aimed at the magnetochemistry of metal complexes of thiosemicarbazones, and that too were concerned with the complexes of bisttltioscinicarbazones). However, as far as the monothiosemicarbazones are concerned, the magnetochemistry of transition metal complexes of di-2-pyridyl ketone thiosemicarbazones turned up quite unexplored. Consequently, an investigation into it appeared novel and promising to us and that prompted this study, which can be regarded as the initial step towards exploring the magnetochemistry of thiosemicarbazone complexes, especially of di-2-pyridyl ketone derivatives.We could successfully isolate single crystals suitable for X-ray diffraction for the first three ligands. To conclude, we have synthesized some new thiosemicarbazones and their transition metal complexes and studied their structural, spectral and magnetic attributes. Some ofthe complexes revealed interesting stereochemistries and possible bridging characteristics with spectroscopic evidences. Unfortunately, single crystal Xray diffraction studies could not be carried out for many of these interesting compounds due to the lack of availability of suitable quality single crystals. However, the magnetic studies provided support for the proposed stereochemistry giving evidences for their magnetically concentrated nature. The magnetic susceptibilities measured at six different temperatures in the 80-298 K range are fitted into different magnetic equations, which provided an idea about the magnetic behavior of the compounds under study. Some of the copper, oxovanadium, nickel and cobalt complexes are found to possess anomalous magnetic moments, i.e., they revealed no regular gradation with temperature. However, some other copper complexes are observed to be antiferromagnetic, due to super-exchange pathways. The manganese complexes and one of the cobalt complexes are also observed to be antiferromagnetic in nature. However, some nickel complexes have turned up to be ferromagnetic. Accordingly, the versatile stereoehemistry and magnetic behavior of the complexes studied, prompt us to conclude that the transition metal complexes of di-2-pyridyl ketone thiosemicarbazones are promising systems for potential magnetic applications.

Chemistry of molecular and supramolecular structures of vanadium(IV) and dioxygen-bridged V(V) complexes incorporating tridentate hydrazone ligands

Four hydrazone ligands: 2-benzoylpyridine benzoyl hydrazone (HBPB), di-2-pyridyl ketone nicotinoyl hydrazone (HDKN), quinoline-2-carbaldehyde benzoyl hydrazone (HQCB), and quinoline-2-carbaldehyde nicotinoyl hydrazone (HQCN) and four of their complexes with vanadyl salts have been synthesized and characterized. Single crystals of HBPB and complexes [VO(BPB)(l2-O)]2 (1) and [VO(DKN)(l2-O)]2 ½H2O (2) were isolated and characterized by X-ray crystallography. Each of the complexes exhibits a binuclear structure where two vanadium(V) atoms are bridged by two oxygen atoms to form distorted octahedral structures within cis-N2O4 donor sets. In most complexes, the uninegative anions function as tridentate ligands, coordinating through the pyridyl- and azomethine-nitrogen atoms and enolic oxygen whereas in complex [VO(HQCN)(SO4)]SO4 4H2O (4) the ligand is coordinated in the keto form. Complexes [VO(QCB)( OMe)] 1.5H2O (3) and 4 are found to be EPR active and showed well-resolved axial anisotropy with two sets of eight line pattern

Functions satisfying holonomic q-differential equations

In a similar manner as in some previous papers, where explicit algorithms for finding the differential equations satisfied by holonomic functions were given, in this paper we deal with the space of the q-holonomic functions which are the solutions of linear q-differential equations with polynomial coefficients. The sum, product and the composition with power functions of q-holonomic functions are also q-holonomic and the resulting q-differential equations can be computed algorithmically.

Algorithmen für q-holonome Funktionen und q-hypergeometrische Reihen

Die q-Analysis ist eine spezielle Diskretisierung der Analysis auf einem Gitter, welches eine geometrische Folge darstellt, und findet insbesondere in der Quantenphysik eine breite Anwendung, ist aber auch in der Theorie der q-orthogonalen Polynome und speziellen Funktionen von großer Bedeutung. Die betrachteten mathematischen Objekte aus der q-Welt weisen meist eine recht komplizierte Struktur auf und es liegt daher nahe, sie mit Computeralgebrasystemen zu behandeln. In der vorliegenden Dissertation werden Algorithmen für q-holonome Funktionen und q-hypergeometrische Reihen vorgestellt. Alle Algorithmen sind in dem Maple-Package qFPS, welches integraler Bestandteil der Arbeit ist, implementiert. Nachdem in den ersten beiden Kapiteln Grundlagen geschaffen werden, werden im dritten Kapitel Algorithmen präsentiert, mit denen man zu einer q-holonomen Funktion q-holonome Rekursionsgleichungen durch Kenntnis derer q-Shifts aufstellen kann. Operationen mit q-holonomen Rekursionen werden ebenfalls behandelt. Im vierten Kapitel werden effiziente Methoden zur Bestimmung polynomialer, rationaler und q-hypergeometrischer Lösungen von q-holonomen Rekursionen beschrieben. Das fünfte Kapitel beschäftigt sich mit q-hypergeometrischen Potenzreihen bzgl. spezieller Polynombasen. Wir formulieren einen neuen Algorithmus, der zu einer q-holonomen Rekursionsgleichung einer q-hypergeometrischen Reihe mit nichttrivialem Entwicklungspunkt die entsprechende q-holonome Rekursionsgleichung für die Koeffizienten ermittelt. Ferner können wir einen neuen Algorithmus angeben, der umgekehrt zu einer q-holonomen Rekursionsgleichung für die Koeffizienten eine q-holonome Rekursionsgleichung der Reihe bestimmt und der nützlich ist, um q-holonome Rekursionen für bestimmte verallgemeinerte q-hypergeometrische Funktionen aufzustellen. Mit Formulierung des q-Taylorsatzes haben wir schließlich alle Zutaten zusammen, um das Hauptergebnis dieser Arbeit, das q-Analogon des FPS-Algorithmus zu erhalten. Wolfram Koepfs FPS-Algorithmus aus dem Jahre 1992 bestimmt zu einer gegebenen holonomen Funktion die entsprechende hypergeometrische Reihe. Wir erweitern den Algorithmus dahingehend, dass sogar Linearkombinationen q-hypergeometrischer Potenzreihen bestimmt werden können. ________________________________________________________________________________________________________________

Ferrocene-Based Pyridylphosphine Ligands – Coordination Chemistry of Group 10, 11 and 12 Metals

English: The present thesis describes the synthesis of 1,1’-ferrocendiyl-based pyridylphosphine ligands, the exploration of their fundamental coordination chemistry and preliminary experiments with selected complexes aimed at potential applications. One main aspect is the synthesis of the bidentate ferrocene-based pyridylphosphine ligands 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene, 1-(Pyrid-3-yl)-1’-diphenylphosphinoferrocene and 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene. A specific feature of these ligands is the ball-bearing like flexibility of the ferrocenebased backbone. An additional flexibility element is the rotation around the C–C single bonds. Consequently, the donor atoms can realise a wide range of positions with respect to each other and are therefore able to adapt to the coordination requirements of different metal centres. The flexibility of the ligand also plays a role in another key aspect of this work, which concerns the coordination mode, i. e. bridging vs. chelating. In addition to the flexibility, also the position of the donor atoms to each other is important. This is largely affected by the position of the pyridyl nitrogen (pyrid-2-yl vs. pyrid-3-yl) and the methylen group in 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene. Another interesting point is the combination of a soft phosphorus donor atom with a harder nitrogen donor atom, according to the HSAB principle. This combination generates a unique binding profile, since the pi-acceptor character of the P site is able to stabilise a metal centre in a low oxidation state, while the nitrogen sigma-donor ability can make the metal more susceptible to oxidative addition reactions. A P,N-donor combination can afford hemilabile binding profiles, which would be ideal for catalysis. Beyond 1,2-substituted ferrocene derivatives, which are quite successful in catalytic applications, 1,1’-derivatives are rather underrepresented. While a low-yield synthetic pathway to 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene was already described in the literature [I. R. Butler, Organometallics 1992, 11, 74.], it was possible to find a new, improved and simplified synthetic pathway. Both other ligands were unknown prior to this work. Satisfactory results in the synthesis of 1-(Pyrid-3-yl)-1’-diphenylphosphinoferrocene could be achieved by working in analogy to the new synthetic procedure for 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene. The synthesis of 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene has been handled by the group of Prof. Petr Stepnicka from Charles University, Prague, Czech Republic. The synthesis of tridentate ligands with an analogous heterodentate arrangement, was investigated briefly as a sideline of this study. The major part of this thesis deals with the fundamental coordination chemistry towards transition metals of the groups 10, 11 and 12. Due to the well-established catalytic properties of analogous palladium complexes, the coordination chemistry towards palladium (group 10) is of particular interest. The metals zinc and cadmium (group 12) are also of substantial importance because they are redox-inert in their divalent state. This is relevant in view of electrochemical investigations concerning the utilisation of the ligands as molecular redox sensors. Also mercury and the monovalent metals silver and gold (group 11) are included because of their rich coordination chemistry. It is essential to answer questions concerning aspects of the ligands’ coordination mode bearing in mind the HSAB principle.

An update of the mechanisms of resistance to EGFR-tyrosine kinase inhibitors in breast cancer: gefitinib (Iressatrade mark)-induced changes in the expression and nucleo-cytoplasmic trafficking of HER-ligands (Review)

Intrinsic resistance to the epidermal growth factor receptor (EGFR; HER1) tyrosine kinase inhibitor (TKI) gefitinib, and more generally to EGFR TKIs, is a common phenomenon in breast cancer. The availability of molecular criteria for predicting sensitivity to EGFR-TKIs is, therefore, the most relevant issue for their correct use and for planning future research. Though it appears that in non-small-cell lung cancer (NSCLC) response to gefitinib is directly related to the occurrence of specific mutations in the EGFR TK domain, breast cancer patients cannot be selected for treatment with gefitinib on the same basis as such EGFR mutations have been reported neither in primary breast carcinomas nor in several breast cancer cell lines. Alternatively, there is a general agreement on the hypothesis that the occurrence of molecular alterations that activate transduction pathways downstream of EGFR (i.e., MEK1/MEK2 - ERK1/2 MAPK and PI-3'K - AKT growth/survival signaling cascades) significantly affect the response to EGFR TKIs in breast carcinomas. However, there are no studies so far addressing a role of EGF-related ligands as intrinsic breast cancer cell modulators of EGFR TKI efficacy. We recently monitored gene expression profiles and sub-cellular localization of HER-1/-2/-3/-4 related ligands (i.e., EGF, amphiregulin, transforming growth factor-α, ß-cellulin, epiregulin and neuregulins) prior to and after gefitinib treatment in a panel of human breast cancer cell lines. First, gefitinibinduced changes in the endogenous levels of EGF-related ligands correlated with the natural degree of breast cancer cell sensitivity to gefitinib. While breast cancer cells intrinsically resistant to gefitinib (IC50 ≥15 μM) markedly up-regulated (up to 600 times) the expression of genes codifying for HERspecific ligands, a significant down-regulation (up to 106 times) of HER ligand gene transcription was found in breast cancer cells intrinsically sensitive to gefitinib (IC50 ≤1 μM). Second, loss of HER1 function differentially regulated the nuclear trafficking of HER-related ligands. While gefitinib treatment induced an active import and nuclear accumulation of the HER ligand NRG in intrinsically gefitinib-resistant breast cancer cells, an active export and nuclear loss of NRG was observed in intrinsically gefitinib-sensitive breast cancer cells. In summary, through in vitro and pharmacodynamic studies we have learned that, besides mutations in the HER1 gene, oncogenic changes downstream of HER1 are the key players regulating gefitinib efficacy in breast cancer cells. It now appears that pharmacological inhibition of HER1 function also leads to striking changes in both the gene expression and the nucleo-cytoplasmic trafficking of HER-specific ligands, and that this response correlates with the intrinsic degree of breast cancer sensitivity to the EGFR TKI gefitinib. The relevance of this previously unrecognized intracrine feedback to gefitinib warrants further studies as cancer cells could bypass the antiproliferative effects of HER1-targeted therapeutics without a need for the overexpression and/or activation of other HER family members and/or the activation of HER-driven downstream signaling cascades

COMP1205 Student Presentations Q-T

Monday 12th May Building 34 Room 3001, 10.00-12.45 Su & Rikki Presenting: Groups: Q, R, S, T Marking Groups: U, V, W, X Schedule and Topics 10.00-10.05: Introduction and protocol for the session 10.05-10.25 Group Q: Disablitites and rights – legal responsibilities 10.25-10.45 Group R: Computer Ethics, Professional bodies and accreditation 10.45-11.05 Group S: Digital divide 11.05-11.25 Group T: How the web is chaning the world: co-operation, co-creation, crowd funding and crowd sourcing 11.25-11.45: Wash-up: feedback session for presentation groups