Synthesis and Chemistry of Multidentate Mixed Donor Ligands PDF Download
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Author: Ian James Luck
Publisher:
ISBN:
Category : Ligands
Languages : en
Pages : 490
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Author: Ian James Luck
Publisher:
ISBN:
Category : Ligands
Languages : en
Pages : 490
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Author: Rajarshi Mondal
Publisher:
ISBN:
Category :
Languages : en
Pages : 0
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This project explored the synthesis of bi-functional neutral donor ligands using pi-extended phenanthridine system which can stabilize the late transition metals. My interest would be the phenanthridine ring of 14 pi-electron polycyclic heteroaromatic system, which is the building block of my ligands and the properties of this extended aromatic system while binding with late transition metals and comparing with smaller congener quinoline precursor for understanding the effect of site dependent pi extension. The application and properties of designed metal complexes have been extensively studied. The study of using pi-extended phenanthridine as a ligand and its metal complexes would open a new window of opportunities. A synthetic route to bromo functionalization of benzo-fused N-heterocyclic phenanthridine, enabling the constructions of both phosphinophenanthridine and NHC carbene-phenanthridine have been devised, which are heterobifunctional Lewis base containing both phosphine/carbene and phenanthridine donors. The coordination chemistry for both phosphine/carbene ligands with ions of late first-row transition metals has been explored. 4-Bromophenanthridine was synthesized by Suzuki cross-coupling/condensation, 6-substitution was conducted by reaction between phenanthridinone and phosphine(V) oxyhalide. The installation of phosphine was directed by lithium-halogen exchange of 4-bromophenanthridine. The carbenes were placed by the reaction between 6-halophenanthridine and corresponding imidazole in high temperature. A series of halide bridge Cu complexes were synthesized using phosphino-phenanthridine ligand to check the effect of site selective pi-extension on emission property by comparing with smaller congener quinoline based Cu complexes. Further study leads to design of sterically encumbered phenanthridine for diminishing the excited state geometric orientation. A relative effect of counterion in solid-state emission lifetime has also been studied. A group of octahedral d8 metal complexes were synthesized by using both phosphine/carbene ligands to study the metal to ligand charge transfer and its lifetime. The potential of these complexes for use in the field of photosensitizer was also discussed. Phosphino ligand based Fe complexes have been synthesized and their use in the filed of hydrogenation catalysis has also been discussed.
Author: Dominic P. Halbach
Publisher:
ISBN:
Category : Ruthenium compounds
Languages : en
Pages : 390
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Author: Aaron M. Lineberry
Publisher:
ISBN:
Category : Chemistry
Languages : en
Pages : 153
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Given the continued interest in the use of enantioselective metal-catalyzed asymmetric reactions in organic synthesis, there have been considerable research efforts in the development of new chiral ligands consisting of mixed-donor heteroatoms. This dissertation involves the microwave-assisted synthesis of amino acid-derived pyrrolidine thioethers, as well as a thiolane-based analogue consisting of meso frameworks as opposed to the conventional C2 symmetry found in most chiral ligands. Chapter I of this work gives a brief literature review in the synthesis and applications of pyrrolidine-based ligand systems. Also discussed is a review of 3-pyrroline derivatives, which are an important class of heterocycles used as precursors in the synthesis of 3,4-disubstituted pyrrolidines, as well as several synthetic approaches towards their preparation. Chapter II of this work describes the microwave-assisted synthesis of a series of chiral amino acid-derived pyrrolidine diols, from the appropriate L-amino acid methyl ester hydrochlorides (Leu, Val, Phe) or benzyl esters (Gly, Ala, Ser) and cis-1,4-dichloro-2-butene. The enantiopurity of the chiral 3-pyrroline intermediates have been established through Mosher ester synthesis and by comparison of optical rotation of the amino acid esters. Also, the attempted conversion of the diols into thioethers is discussed. The multi-step synthesis of thiolane analogues, as well as approaches towards novel heterobicyclo[4.3.0]nonanes is discussed. Finally, a modified approach towards the tripodal ligand system [9]aneN2S and a microwave-assisted cyclization of [9]aneN3 are discussed.
Author: Timothy Michael Erasmus Jugovic
Publisher:
ISBN: 9780355341706
Category :
Languages : en
Pages : 132
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Presented in this thesis is the synthesis and characterization of two new classes of mixed donor ligands, as well as several copper(II) and nickel(II) complexes. Chapter II details the synthesis and characterization of thiosemicarbazates, which are tridentate ONS (oxygen, nitrogen, sulfur) donor compounds. In Chapter III complexes of these thiosemicarbazate ligands with nickel(II) and copper(II) are prepared and characterized. Chapter IV discusses the synthesis and characterization of several different amidothiocrown and amidoazathiocrown ethers.
Author: Alexander D. Garnovskii
Publisher: CRC Press
ISBN: 0203911520
Category : Science
Languages : en
Pages : 559
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This reference describes standard and nonstandard coordination modes of ligands in complexes, the intricacies of polyhedron-programmed and regioselective synthesis, and the controlled creation of coordination compounds such as molecular and hn-p-complexes, chelates, and homo- and hetero-nuclear compounds. It offers a clear and concise review of modern synthetic techniques of metal complexes as well as lesser known gas- and solid-phase synthesis, electrosynthesis, and microwave and ultrasonic treatment of the reaction system. The authors pay special attention to o-hydroxyazomethines and their S-, Se-containing analogues, b-diketones, and quinines, among others, and examine the immediate interaction of ligands and metal salts or carbonyls.
Author: Jessica Marie Hanley
Publisher:
ISBN:
Category :
Languages : en
Pages : 194
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Mixed-donor ligands are particularly attractive in inorganic chemistry due to their steric and electronic versatility and the multiple coordination modes they may exercise when bound to metal centers. Although pyridines are arguably the most common nitrogen-donor ligands and the coordination chemistry of heterocyclic thiones is well-established, the reactivity of simple tridentate ligands containing a combination of such functionalities is virtually unknown. The synthesis and reactivity of two new mixed-donor ligands, the bis(pyridyl)mercaptoimidazole (2-py)2m, and the bis(picolyl)mercaptoimidazole (2-pic)2m, have been developed. Several coordination complexes of (2-py)2m and (2-pic)2m have been prepared and fully characterized, including the complete series of group 12 metal compounds {(2-py)2m}MX2 and {(2-pic)2m}MX2 (M = Zn, Cd, Hg; X = CI, Br, I). In addition, an investigation of the coordination of these two N2S donor ligands with copper(I) was pursued because one of the key goals of this project is the preparation of synthetic analogues of methanobactin (mb), a small protein responsible for the uptake and delivery of copper(I) ions to various copper-dependent enzymes such as the particulate form of methane monooxygenase (pMMO). The copper(I) derivatives {(2-py)2m}CuX (X = Br, I) and {(2-pic)2m}CuX (X.
Author: Tia Louise Walker
Publisher:
ISBN:
Category : Chemistry
Languages : en
Pages : 287
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Following the structural characterization and analysis of Blue Copper Proteins (BCP's), macrocyclic ligands have attracted much interest as simple models for naturally occurring metal-macrocycle centers. Presented in this dissertation are the syntheses and characterization of small, simple organic analogs of BCP's. Chapter I of this work gives a brief literature review of Blue Copper Proteins, including their unique spectral characteristics. The synthesis and characterization of several linear and cyclic molecular analogs will be discussed including polythiaethers,3 polyazacycloalkanes,4 thia-aza5 and trithiaethers. The macrocyclic effect will be explained and why cyclic molecular analogs are of current interest. Presented in the second chapter are the syntheses of two 14-membered rings with a 2,3,2,3 altering carbon chain arrangement for 1,8-dithia-4,11-diazacyclotetradecane and 1,11-dithia-4,8-diazacyclotetradecane. The 1,8-dithia-4,11-diazacyclotetradecane is complexed to both Cu2+ and Cu+ and fully characterized using UV-Vis, EPR and CV. The 1,11-dithia-4,8-diazacyclotetradecane was synthesized for structural X-ray comparison of the Cu2+ metal ion. The 1,8-dithia-4,11-diazacyclotetradecane having two nitrogen atoms also makes it attractive for functionalization. Presented in the third chapter of this dissertation is the expansion of these ligands for use as cryptands. The syntheses of two cryptands are fully described and include crystallographic data. One of the cryptand ligands, 1,8-dithia-4,11,18,21-tetraazatricyclo[10.6.6]pentacosane-25-one was successfully complexed to Cu2+ and those results are also discussed. To further conclude this research is a pendant arm derivative and its synthesis. Each nitrogen atom of 1,8-dithia-4,11-diazacyclotetradecane is functionalized with a four carbon chain connecting to 1,4-diaza-7-thiacyclononane.
Author: Jessica Lauren Bongiovanni
Publisher:
ISBN:
Category :
Languages : en
Pages : 248
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A new mixed-donor ligand containing both pyridine and thione donor groups, o-(3-methyl-2-mercaptoimidazolyl)pyridine (o-mpyMe), has been synthesized. The ligand has good solubility and stability in organic solvents, as well as partial solubility in water. The coordination chemistry of this new ligand with metals such as manganese(I), rhenium(I), cobalt(II), nickel(II), copper(I), silver(I), zinc(II), cadmium(II), mercury(II), indium(III), antimony(III) and bismuth(III), leading to an assortment of coordination modes and reactivity. Most significantly, copper(I) complexes of o-mpyMe were prepared with the aim of generating potential synthetic analogues of the metal center in methanobactin, a copper-binding compound. Methanobactin (mb) is responsible for the uptake and transport of copper to the enzyme methane monooxygenase (MMO), which oxidizes methane gas to methanol in the global carbon cycle. The active site of mb consists of a tetrahedral Cu(I) center with N2S2 coordination. Characterization, reactivity and biological activity of [Cu(o-mpyMe)2]X (X = BF4, PF6) to determine if these complexes are viable analogues of methanobactin has been carried out.
Author: Martina Whitehead
Publisher:
ISBN:
Category :
Languages : en
Pages :
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Described herein, is the synthesis and coordination chemistry of seven novel ligands L1 - L7. These ligands form metallosupramolecular assemblies upon coordination of transition metal ions resulting in heterodi- and hetreotrimetallic double helicates and penta- and tetranuclear cyclic helicates. Described in Chapter 2 is a new class of ditopic segmental pyridyl-thiazole(py-tz) N-donor ligands L1 - L3. Reaction of L1 with ZnII ions results in the formation of a dinuclear double helicate [Zn2(L1)2]4+. Reaction of L2 with either ZnII or HgII results in the formation of the L2-containing dinuclear double helicates [Zn2(L2)2]4+ and [Hg2(L2)2]4+. However, reaction with both ZnII or HgII results in the sole formation of the heterodimetallic helicate [HgZn(L2)2]+. Both metal ions are 6-coordinate but the HgII ion is coordinated by the two py-tz-py units whereas the ZnII ion is coordinated by the py-py-tz domain. The reason that these isomeric sites have different preferences for each of the metal ions is due to the position of the thiazole unit within the terdentate domains, as in the central position the thiazole unit increases the?bite angle? of the donor unit making it more suitable for the larger HgII. Conversely the py-py-tz domain has a smaller bite angle and it more suited to the smaller ZnII ion. Reaction of L3 with ZnII, HgII and CuII results in the formation of a heterometallic trinuclear double helicate [HH-[HgCuZn(L3)2]5+. In a similar fashion to L2, the ZnII ion coordinated by the terdentate py-py-tz domain and the HgII coordinated by the py-tz-py domain. The central bipyridine unit coordinates the tetrahedral CuII ion resulting in the first reported example of a heterotrimetallic double helicate. Described in Chapter 4 is a potentially hexadentate N-donor ligand L4, which upon reaction with CdII results in the formation of a dinuclear double helicate [Cd2(L4)2]4+. In this structure the ligand partitions into two tridentate tz-py-py domains each of which coordinate a different metal ion. However, reaction of L4 with ZnII results in the formation of a pentanuclear circular helicate [Zn5(L4)5]10+, with all the five zinc ions adopting a octahedral coordination geometry arising from the coordination of the two tridentate tz-py-py domains from two different ligand strands. This difference in structure is attributed to unfavourable steric interactions which prevent the formation of [Zn2(L4)2]4+ but these unfavourable interactions are not present with the larger Cd2+ ion. Described in Chapter 5 are the potentially pentadentate and tetradentate ligands L5 and L6, respectively. The ligand L5 contains both a bidentate and tridentate binding site separated by a phenylene spacer unit. Reaction of L5 with CuII results in the formation of a pentanuclear circular helicate [Cu5(L5)5]10+. Each of the CuII ions adopts a 5-coordinate geometry formed by coordination of the bidentate domain of one ligand strand and the tridentate domain of a different ligand. As a result this gives a head-to-tail pentanuclear double helicate. Reaction of L6 and L4 (Chapter 4) with CuII results in the formation of a heteroleptic pentanuclear circular helicate [Cu5(L4)3(L6)2]10+. The cyclic array consists of five copper(II) ions, coordinated by three strands of L4 and two strands of L6. In this species four of the CuII adopt a 5- coordinate geometry arising from coordination of a tridentate domain from L4 and a bidentate domain from L6. The remaining copper ion is coordinated by two tridentate domains from L4 resulting in an octahedral coordination geometry. Described in Chapter 6 is the potentially hexadentate N-donor ligand L7 which comprises of two identical tridentate py-py-tz N3 binding domains separated by a pyrene unit. Reaction of L7 with ZnII results in the formation of a tetranuclear circular helicate [Zn4(L7)4]8+ with all four zinc metal ions adopting a six-coordinate geometry arising from the coordination of two tridentate pypy- tz units from two different ligand strands. The formation of this lower nuclearity species (e.g. tetranuclear rather than pentanuclear) is attributed to the p-stacking between the pyrene unit and the py-py-tz domain.
