Amine, Amido, and Imido Complexes of Tantalum Supported by a Pyridine-Linked Bis(phenolate) Pincer Ligand: Ta−N π-Bonding Influences Pincer Ligand Geometry

A series of tantalum imido and amido complexes supported by a pyridine-linked bis(phenolate) ligand has been synthesized. Characterization of these complexes via X-ray crystallography reveals both C_s and C_2 binding modes of the bis(phenolate)pyridine ligand, with complexes containing two or fewer strong π-donor interactions from ancillary ligands giving C_s symmetry, whereas three strong π-donor interactions (e.g., three amido ligands or one amido ligand and one imido ligand) give C_2-symmetric binding of the bis(phenolate)pyridine ligand. DFT calculations and molecular orbital analyses of the complexes have revealed that the preference for C_s-symmetric ligand binding is a result of tantalum−phenolate π-bonding, whereas in cases where tantalum−phenolate π-bonding is overridden by stronger Ta−N π-bonding, C_2-symmetric ligand binding is preferred, likely because conformationally this is the lowest-energy arrangement. This electronically driven change in geometry indicates that, unlike analogous metallocene systems, the bis(phenolate)pyridine pincer ligand is not a strong enough π-donor to exert dominant control over the electronic and geometric properties of the complex

Development of highly selective ligands for separations of actinides from lanthanides in the nuclear fuel cycle

This account summarizes recent work by us and others on the development of ligands for the separation of actinides from lanthanides contained in nuclear waste streams in the context of a future European strategy for nuclear waste management. The current status of actinide/lanthanide separations worldwide is briefly discussed, and the synthesis, development, and testing of different classes of heterocyclic soft N- and S-donor ligands in Europe over the last 20 years is presented. This work has led to the current benchmark ligand that displays many of the desirable qualities for industrial use. The improvement of radiolytic stability through ligand design is also discussed

Expansion of the ligand knowledge base for chelating P,P-donor ligands (LKB-PP)

[Image: see text] We have expanded the ligand knowledge base for bidentate P,P- and P,N-donor ligands (LKB-PP, Organometallics2008, 27, 1372–1383) by 208 ligands and introduced an additional steric descriptor (nHe(8)). This expanded knowledge base now captures information on 334 bidentate ligands and has been processed with principal component analysis (PCA) of the descriptors to produce a detailed map of bidentate ligand space, which better captures ligand variation and has been used for the analysis of ligand properties

Cobalt(II) and Nickel(II) Complexes of Aroyl Hydrazone Ligand: Synthesis and Characterization

Abstract The remarkable biological activity of acid hydrazides R–CO–NH–NH2, their corresponding aryolhydrazones R–CO–NH–N=CHR, and also their mode of chelation with transition metal ions has aroused interest in the past due to possible biomimetic applications. Hydrazone Schiff bases and their Cobalt and Nickel complexes have a variety of applications in biological, clinical and analytical fields. Recently there has been a considerable interest in the coordination chemistry of transition metals especially, Cobalt and Nickel with O-N donor hydrazone ligands because of their potential biological and pharmacological applications. The coordination compounds of aroylhydrazones have been reported to act as enzyme inhibitors and are useful due to their pharmacological applications. From last one year I have been studying the chemistry of transition metal complexes with O-N containing donor environments. In this dissertation I report the synthesis and full characterization of several O-N donor Schiff’s base hydrazone ligands and their corresponding cobalt complexes. The single crystal x-ray studies of synthesized Co complexes (1-3) are under process with our collaborator. One of the three synthesized Co compound (complex 2) is successfully characterized by X-ray crystallography. But due to incomplete refinement of x-ray date I am unable to show the x-ray structure in this dissertation. I also report the synthesis of some Nickel complexes of corresponding O-N donor hydrazone ligands but due to shortage of time am unable to present the characterization data in this thesis. Key words: Hydrazone Lgand; O-N donor systems; Cobalt complexes; Nickel Complexe

Structural studies on the interactions of a P2N tridentate ligand with copper(I) silver(I) and S : a dissertation presented in partial fulfilment of the degree of Master of Philosophy at Massey University

This thesis presents a study of the coordination chemistry, chemical reactivity, spectroscopy, structure and bonding of the hybrid polydentate ligand 2-(diphenylphosphino)-N-[2-(diphenylphosphino)benzylidene]benzeneamine (PNCP) with copper(I), silver(I) and sulfur. The hybrid polydentate (PNCP) ligand contains two inequivalent phosphorus (soft) and one nitrogen (hard) donor atoms, Chapter One is a brief overview of tertiary phosphines used as monodentate, bidentate, tridentate and polydentate ligands with transition metals. In Chapter Two, the preparation structure and characterisation of PNCP have been studied. Reactions of PNCP with sulphur have been investigated and a small site selectivity for one of the P atoms noted. Experiments have also included selective synthesis of the unsymmetrical mono-sulphide tertiary phosphine ligands SPNCP, PNCPS and of the di-sulfide SPNCPS ligand, as well as a study on the molecular structure of the 3-coordinate complex, [Cu(SPNCPS)]CIO₄. In Chapter Three the preparation of a series of copper(I) complexes of the general formula [Cu(PNCP)ClO₄] and [Cu(PNCP)L]ClO₄ (L- ligands containing S, N donor atoms) have been reported. The crystal structure of [Cu(PNCP)ClO₄] has been determined, and shows PNCP acts as a tridentate ligand coordinated to copper(I) via two phosphorus and one nitrogen donor atoms. The copper(I) atom has a distorted tetrahedral environment with two short Cu-P bonds and a slightly long Cu-N bond. In Chapter Four, studies on the preparation of the mononuclear complex [Ag(PNCP)ClO₄] and the dinuclear complex [Ag(PNCP)(SCN)]₂ are presented. Both complexes were characterized by a variety of physicochemical techniques. The tridentate behaviour of PNCP in the complex [Ag(PNCP)ClO₄] was established but the Ag-N bond was long and weak. In the complex [Ag(PNCP)(SCN)]₂ the Ag-N bond not exist and PNCP acts as a bidentate ligand

Synthesis and reactivity of gold(III) complexes containing cycloaurated iminophosphorane ligands

Transmetallation reactions of ortho-mercurated iminophosphoranes (2-ClHgC₆H₄)Ph₂P NR with [AuCl₄]⁻ gives new cycloaurated iminophosphorane complexes of gold(III) (2-Cl₂AuC₆H₄)Ph₂P NR [R = (R,S)- or (S)-CHMePh, p-C₆H₄F, tBu], characterised by NMR and IR spectroscopies, ESI mass spectrometry and an X-ray structure determination on the chiral derivative R = (S)-CHMePh. The chloride ligands of these complexes can be readily replaced by the chelating ligands thiosalicylate and catecholate; the resulting derivatives show markedly higher anti-tumour activity versus P388 murine leukaemia cells compared to the parent chloride complexes. Reaction of (2-Cl₂AuC₆H₄)Ph₂P NPh with PPh₃ results in displacement of a chloride ligand giving the cationic complex [(2-Cl(PPh₃)AuC₆H₄)Ph₂P NPh]⁺, indicating that the P N donor is strongly bonded to the gold centre

Synthesis and Characterization of Oxomolybdenum(VI) Complexes with Aroyl Hydrazones of Benzil and Diacetyl Monooxime

Mo(VI) complexes of selected ONO donor ligands may mimic the active sites of some oxotransfer molybdoenzyme and hence it is of great interest in bio-inorganic chemistry. I have been studying the chemistry molybdenum with O-N containing donor environments since one year. In this dissertation I have reported the synthesis and characterization of several O-N Schiff base hydrazone ligands and their corresponding oxomolybdenum(VI) complexes. All the synthesized ligands and corresponding Mo(VI) complexes has been characterized by several spectroscopic (IR, UV-Vis) technique and redox properties were explored by cyclic voltammetry

Bioavailability of metals species in water ecosystem

Koncentrace volných kovových iontů je často jen malou částí celkové koncentrace kovu v prostředí. Přes tento malý obsah, je ve většině případů koncentrace volných kovových iontů klíčovým faktorem při určování biodostupnosti a toxicity pro organizmus. Membránová technika Donnan se používá k měření koncentrace volných kovových iontů a v této diplomové práci je ověřena pro směsi kovů (Pb + Cu) při absenci a přítomnosti malých organických ligandů. Olovo a měď jsou environmentálně důležité kovy díky své toxicitě a rozdílným vazebným vlastnostem ve vztahu ke studovaným ligandům.The free metal ion concentration is often only a small fraction of the total metal concentration in the environment. Despite their small amount, in most of the circumstances the free metal ion concentration is the key factor in determining metal bioavailability and toxicity for the organisms. The Donnan membrane technique is able to measure the free metal ion concentration and in this thesis, it is validated for metal mixtures (Pb + Cu) in absence and presence of small organic ligand mixtures. Lead and copper are environmental relevant metals due to their toxic properties and different binding properties relative to the studied ligands.