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Sze-To, Lap, and 司徒立. "The structural chemistry of coordination compounds containing d-block or f-block metals." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2010. http://hub.hku.hk/bib/B45204470.
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Ghebregziabiher, Berhe Haile. "Synthesis of chiral thiourea ligands and their transition metal complexes." Thesis, Stellenbosch : Stellenbosch University, 2003. http://hdl.handle.net/10019.1/53610.
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Thesis (MSc)--Stellenbosch University, 2003.ENGLISH ABSTRACT: Modification of chitosan with benzoylisothiocyanate was attempted, however due to solvent problem the study was left incomplete till appropriate solvent is designed. N,N-diethyl-N -camphanoylthiourea (HL8), N-piperidyl-N '-camphanoylthiourea (HL9), N-pyrrolidyl-N -camphanoylthiourea (HL10) and N,N-diethyl-N -adamantylcarbonyl thiourea (HL11)have been synthesised and characterised for the first time. Two of these ligands HL8 and HL11, were used to form a number of transition metal complexes, namely H30+{fae-[Co(L8-S,Obn, cis-[Ni(L8-S,0)2], trans-[Cu(L8-S,0)2], translcis-[Zn(L 8_S,0)2], translcis-[Pt(L 8_S,0)2], Ag2[(HL8-S)(L-J.1-S,O)]2, translcis- [Ni(L11-S,O)2]and translcis-[Cu(L11_S,O)2]. The new products are fully characterised by means of MS, IR spectroscopy, NMR spectroscopy, elemental (C, H, Nand S) analysis and melting point determinations. The H30+{fae-[Co(L8-S,Obn, cis-[Ni(L8- S,O)2], trans-[Cu(L8-S,O)2] and Ag2[(HL8-S)(L-J.1-S,O)]2 are also characterised by Xray diffraction analysis. The structure of the new chiral N,N-dialkyl-N' -camphanoylthiourea ligand (HL8) has a significant effect on its coordination chemistry with transition metal ions. This ligand forms H30+ {fae-[Co(L8-S,Obn, cis-[Ni(L8-S,0)2], trans-[Cu(L-S,O)2] and Ag2[(HL8- S)(L8-J.1-S,O)]2 complexes with the Co(II), Ni(II), Cu(II) and Ag(I) metal ions respectively. The spectroscopic and X-ray diffraction results of these complexes indicate a bidentate mode of coordination of the ligand (with its Sand °donor atoms) to the Co(II), Ni(II) and Cu(II) metal ions. The reaction of this ligand with silver(I) however affords the formation of a binuclear silver(I) complex exhibiting monodentate and bidentate modes of coordination within the same complex. The exclusive formation of trans-[Cu(L8-S,0)2] is a new phenomenon for the HL type thiourea ligands with Sand °donor atoms. Up to this point a maximum of 15 % trans-isomer has been reported in ltterature." All the transition metal complexes made with HL8and HL11are air stable in both the liquid and solid states except the H30+{fae-[Co(L 8-S,Ob]} Interestingly the deep green fae- H30+{fae-[Co(L8-S,Obn complex is air sensitive and the Co(II) oxidizes to Co(III) in the complex by atmospheric O2. The oxidation of Co(II) to Co(III) in the complex is confirmed by 1Hand 13CNMR spectra as well as by UV-Visible spectra of the complex. The NMR spectra of the complexes indicated the presence of one isomer in each complex except for the NMR spectra of the platinum complex of the HL8 ligand. The presence of the minor trans-[Pt(L8-S,Q)21 isomer in combination with the major cis-[Pt(L8-S,Q)21 isomer in the platinum complex was indicated by the 1H, 13Cand 195ptNMR spectra of the complex.
AFRIKAANSE OPSOMMING: Pogings om chitosan met benzoylisothiocyanate te modifiseer is onvoltooid gelaat weens die gebrek aan'n geskikte oplosmiddel. N,N-diethyl-N -carnphanoylthiourea (HL8), N-piperidyl-N -camphanoylthiourea (HL9), N-pyrrolidyl-N -camphanoylthlourea (HL10) en N,N-diethyl-N -adamantylcarbonyl thiourea (HL11) is vir die eerste keer gesintetiseer en gekarakteriseer. Twee van die ligande, HL8 en HL11, is gebruik om verskeie oorgangsmetaalkomplekse te berei, nl. H30+{fac-[Co(L8-S,Ohn, cis-[Ni(L8-S,0)2], trans-[Cu(L8-S,0)2], trans/cis-[Zn(L8 - S,0)2], trans/cis-[Pt(L8-S,0)2], Ag2[(HLB-S)(L-jl-S,0)]2, trans/cis-[Ni(L11-S,0)2] en trans/cis-[Cu(L11_S,0)2]. Die nuwe produkte is volledig gekarakteriseer deur middel van MS, IR spektroskopie, KMR spektrometrie, elemente (C, H, N en S) analise en smeltpuntbepaling. Die komplekse H30+{fao-[Co(L8-S,0)3n, cis-[Ni(L8-S,0)2], trans- [Cu(L8-S,0)2] en Ag2[(HLB-S)(L-jl-S,0)]2 is ook deur middel van X-straaldiffraksieanalise gekarakteriseer. Die struktuur van die nuwe chirale N,N-dialkyl-N'-camphanoylthiourea ligand (HL8) het In beduidende invloed op die koordinasie van hierdie ligand met oorgangsmetaalione. Die ligand vorm H30+{fac-[Co(L8-S,Ohn, cis-[Ni(L8-S,0)2], trans-[Cu(L-S,0)2] en Ag2[(HL8-S)(L8-Il-S,0)]2 komplekse met Co(ll)-, Ni(II)-, Cu(II)- en Ag(I)-ione respektiewelik. Spektroskopiese en X-straaldiffraksie-analise van die komplekse toon dat die ligande op 'n bidentate wyse d.m.v. die S- en O-donoratome met Co(II), Ni(lI) en Cu(lI) koordineer. Die reaksie van hierdie ligand met Ag(I)-ione lei egter tot die vorming van 'n dikernige silwer(I)-kompleks waarin die ligande monodentaat (S) en bidentaat (S en 0) aan die metaal gebind is. Die vorming van uitsluitlik die trans-[Cu(L8-S,0)2] in die reaksie van HL8 met Cu(lI) is 'n besondere fenomeen in die chemie van hierdie tipe ligande; in die literatuur word melding gemaak van slegs een ander trans-kompleks met hierdie ligande, en dan wel met 'n maksimum opbrengs van 15%.29 Alle oorgangsmetaalkomplekse met HLB en HL11 is stabiel indien blootgestel aan lug, ongeag of die verbindings opgelos word of in die vastetoestand verkeer, behalwe H30+{fao-[Co(L8-S,Ohn. Die diep-groen gekleurde H30+{fao-[Co(L8-S,Ohn)3]} kompleks is lugsensitief; Co(lI) word deur lugsuurstof na Co(lIl) ge-oksideer. Die oksidasie in die kompleks kan deur middel van 1H en 13CKMR spektrometrie sowel as UV-sigbare spektrofotometrie bevestig word. Die KMR spektra van alle komplekse dui op die teenwoordigheid van slegs een isomeer in oplossing, behalwe in die geval van die platinum(lI) kompleks met HL8. Die teenwoordigheid van lae konsentrasies trans-[Pt(L8-S,0)2] isomeer tesame met veel hoër konsentrasies van die cis-[Pt(L8 -S,O)2] isomeer word deur 1H, 13Cen 195ptKMR spektroskopie aangedui.
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Habtu, Michael M. "A study of the transport, extraction and co-ordination chemistry of a number of thiourea ligands with a series of transition and post-transition metal ions." Thesis, Stellenbosch : Stellenbosch University, 2003. http://hdl.handle.net/10019.1/97374.
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Thesis (MSc)--Stellenbosch University, 2003.ENGLISH ABSTRACT: In this study, a number of mono- and di-substituted acyl(aroyl)thioureas were investigated for potential application as specific carriers (ionophores) for the transport and extraction of Ag(l) from a mixture of Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(lI) ions. The experimental arrangement for the transport experiments employed a liquid membrane set up involving a 3-phase system - 2 aqueous phases (source and receiving phase) separated by a chloroform membrane incorporating the ligand. Competitive metal ion transport experiments were conducted using the liquid membrane set up. The aqueous source and receiving phases were analyzed using Atomic Absorption Spectroscopy (AAS) and results were confirmed by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICPOES). The transport results show that the N,N-dialkyl-substituted-N'-acyl(aroyl) (HL) thioureas studied, with the exception of the N,N-di-(2-hydroxyethyl)-N'-benzoylthiourea (HL3 ) and N-piperidyl-N'-4-nitrobenzoylthiourea (HL9 ), were efficient and selective for Ag(I). HL9 was also selective for Ag(l) but not efficient. HL3 was selective for Cu(II). Under the experimental conditions employed, 13% Cu(lI) was transported by HL3 . Among the N,Ndialkyl- N'-aroylthioureas, maximum Ag(l) transport was obtained by using N,N-diethyl-N'-4- chlorobenzoylthiourea (HL5 ) and N,N-di-n-butyl-N'-benzoylthiourea (HL \ Under the experimental conditions employed, the percentages of Ag(l) transported by HL5 and HL 1 were 48% and 42% respectively. The transport selectivity and efficiency of 3,3,3' ,3'-tetraethyl-1 ,1'-isophthaloylbisthiourea (H2L12 ) and N,N-diethyl-N'-camphanoylthiourea (HL13)for Ag(l) were also studied. We were particularly interested, in comparing the Ag(l) transport and extraction efficiency of these ligands with that of the HL and H2L ligands. The experimental results reveal that, of all the ligands we investigated in this study, HL 13 was the most efficient and selective carrier for Ag(l) transport. The interesting result is that, depending on the ligand concentration used, HL 13 transported 71-81% of Ag(I). Competitive two-phase metal ion solvent extraction experiments were also performed under conditions similar to the transport studies. The results show that by varying the ligand concentration in the membrane phase, up to 100% Ag(l) can be selectively and efficiently extracted from the mixture of the seven metal ions. Finally, the N,N-di-(n)-butyl-N'-benzoylthiourea (HL1) ligand and its complex with Ag(l) were synthesized. Single crystals of the complex were grown for X-ray crystallography and the crystal and molecular structure of the complex was determined. The crystal structure showed that Ag(l) is bonded to the deprotonated ligand through the S,O atoms forming interesting cluster [Ag (L - S, 0)] 4 in the solid state. This structure is monoclinic and crystallizes in the space group P21!c with a = 17.805 (4) A, b = 21.759 (4) A, c = 36.438 (7) A, f3= 96.34(3)°, Z = 8 and a final R-factor of 5.4%.
AFRIKAANSE OPSOMMING: In hierdie proefskrif is 'n aantal mono- en di-gesubstitueerde asiel(ariel) tioureums ondersoek vir moontlike gebruik as ionofore (spesifieke draers) vir die transportasie en ekstraksie van Ag(l) vanuit 'n mengsel van Co(ll), Ni(II), Cu(II), Zn(II), Cd(II), Ag(l) en Pb(lI) ione. 'n Drie-fase selsisteem is gebruik vir die transportasie eksperimente, twee waterige fases (bron- en ontvang-fase) wat geskei is met die chloroform membraan fase wat die ligande bevat. Kompeterende metaalioon transportasie eksperimente is uitgevoer met behulp van hierdie vloeistof membraan stelsel. Die twee waterige fases is deur middel van Atoomabsorpsie Spektroskopie (AAS) ge-analiseer en resultate is bevestig met gebruik van Induktief-gekoppelde Plasma-Optiese Emissie Spektroskopie (IGP-OES). Die resultate het getoon dat elkeen van die N,N-dialkiel-gesubstitueerde-N'-asiel(ariel) (HL) tioureums, met uitsondering van N,N-di(2-hidroksie-etiel)-N'-benzieltioureum(HL 3) en Npiperidiel- N'-4-nitrobenzieltioureum(HL9 ), doeltreffend en selektief was vir Ag(l) transportasie. HL9 was selektief vir Ag(I), maar die transportasie waarde was nie hoog nie, dws. dit was nie doeltreffend nie. HL3 was selektief vir Cu(II). Met gebruik van ons eksperimentele kondisies is 13% Cu(lI) getransporteer deur HL 3. Van die N,N-dialkiel-N'- ariel tioureums, is maksimum transportasie van Ag(l) verkry met gebruik van N,N-dietiel- N'-4-chlorobenzieltioureum (HL5) en N,N-di-n-butiel-N'-benzieltioureum (HL1). Met gebruik van ons eksperimentele kondisies was die persentasie transportasie van Ag(l) deur HL5 en HL 1 48% en 42% onderskeidelik. Die selektiwiteit en doeltreffendheid van 3,3,3' ,3'-tetra-etiel-1 ,t-isoftaltelblstioureumtl+L 12) en N,N-di-etiel-N'-kamfonieltioureum (HL13) vir Ag(l) transportasie is ook onderneem. Ons was besonder ge-interesseerd om die Ag(l) transportasie en ekstraksie van hierdie ligande te vergelyk met dié van die HL en H2L tipe ligande. Die eksperimentele resultate het getoon dat van al die ligande wat bestudeer is, HL 13 die doeltreffendste en mees selektiewe ionofoor was. Van besondere, belang was dat, afhangend van die ligand konsentrasie wat gebruik is, HL13 71-81% Ag(l) getransporteer het. Kompeterende twee-fase metaalioon vloeistof-vloeistof ekstraksie eksperimente is ook uitgevoer onder toestande soortgelyk aan dié van die transportasie eksperimente. Die resultate toon dat met varierende ligand konsentrasie, tot soveel as 100% Ag(l) selektief en doeltreffend geëkstrakeer word vanuit 'n mengsel van die sewe metaal ione. N,N-di-n-butiel-N'-benzieltioureum (HL1 ) ligande en die kompleks daarvan met Ag(l) is ook gesintetiseer. Enkel-kristalle van die kompleks is verkry en X-straal kristallografiese analiese is onderneem. Die kristalstruktuur toon hoedat Ag(l) gebind is aan die gedeprotoneerde ligand deur die S en Q atome en toon ook interessante [Ag(L-S,Q)]4 groepe in die vaste toestand. Hierdie struktuur is monoklinies en kristaliseer in die ruimtegroep P21!c met a = 17.805(4) Á, b = 21.759(4)Á, c = 36.438(7)Á, P = 96.34(3t, z = 8 en 'n finale R-faktor van 5.4%.
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Schauer, Philip A. "Organometallic synthons for highly conjugated redox-active materials." University of Western Australia. School of Biomedical, Biomolecular and Chemical Sciences, 2009. http://theses.library.uwa.edu.au/adt-WU2009.0166.
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[Truncated abstract] This thesis describes various synthetic approaches toward the synthesis of highly conjugated complexes incorporating multiple transition metal centres. Particular attention is given to the synthesis of mononuclear complexes that allow for the facile assembly of discrete oligo- and poly-nuclear complexes in a controlled, stepwise fashion. Conjugated multi-metallic materials are of interest on account of their unique photophysical and electronic properties, with a particular emphasis on elucidating the nature of intramolecular communication between multiple metal centres. Chapter 1 provides a survey of these topics and current research efforts in the field. Chapter 2 describes the synthesis of Group-VIII allenylidene complexes incorporating a terminal bipyridyl moiety that provides a site for further coordination. The new compound 9-hydroxy-9-ethynyl-4,5-diazafluorene was synthesised, and reaction of this proligand with a coordinatively unsaturated metal fragment yields the allenylidene complexes [MCl(PnP)2=C=C=(4,5-diazafluoren-9-yl)]PF6 (M = Ru, PnP = dppm, dppe, dmpe; M = Os, PnP = dppm) and [CpRu(dppe)=C=C=(4,5-diazafluoren- 9-yl)]PF6. The dmpe-ligated complex is particularly susceptible to decomposition, though it was possible to obtain partial spectroscopic characterisation in addition to a single-crystal X-ray structural determination. The remaining allenylidene complexes are stable compounds readily characterised by standard spectroscopic and electrochemical means, with the bis(diphosphine) complexes characterised by single crystal X-ray structural determinations. ... Reactions of the proligand with [RuCl(PnP)2]+ (PnP = dppm, dppe) led to the isolation of a product spectroscopically consistent with the formation of the target cationic allenylidene complexes, though the complexes were not readily purified and the identity of the accompanying anion was not elucidated. The new compound 4-hydroxy-4- ethynyl-cyclopentadithiophene was also prepared, though the compound was found to be highly unstable and susceptible to rapid decomposition. The derived allenylidene complexes [RuCl(PnP)2=C=C=(4-cyclopentadithiophene)]PF6 (PnP = dppm, dppe) were isolated in a pure form and the complexes stable toward spontaneous decomposition. The thienyl-derived allenylidene complexes were characterised by spectroscopic and electrochemical techniques, with a single-crystal X-ray structural determination undertaken for [RuCl(dppm)2=C=C=(4-cyclopentaditiophene)]PF6. Electrochemical properties are significantly different between the complexes, and also show significant variation between electrodes and solvents. The terminal thienyl substituents are electroactive and show one or two oxidation processes consistent with oligomerisation of the thienyl moiety in dichloromethane solvent, and in acetonitrile solvent cyclic voltammograms are consistent with the deposition of an electroactive film on the electrode surface. The electro-polymerisation of the thienylallenylidene complexes offers a promising new route toward multi-metallic allenylidene complexes.
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Wan, Chun-wai. "Spectroscopic properties and coordination chemistry of d10 metal complexes with the polypyridyl and naphthyridyl ligands /." Hong Kong : University of Hong Kong, 2000. http://sunzi.lib.hku.hk/hkuto/record.jsp?B22227301.
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尹俊偉 and Chun-wai Wan. "Spectroscopic properties and coordination chemistry of d10 metal complexes with the polypyridyl and naphthyridyl ligands." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2000. http://hub.hku.hk/bib/B31223564.
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Lesikar, Leslie Anne. "The synthesis and structural characterization of main group and transition metal complexes supported by nitrogen based ligands." [Fort Worth, Tex.] : Texas Christian University, 2008. http://etd.tcu.edu/etdfiles/available/etd-01162009-164206/unrestricted/Lesikar.pdf.
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Brayshaw, Simon Keith. "Metal complexes bearing pendant alkynes and metal complexes of N-heterocyclic carbenes." University of Western Australia. School of Biomedical and Chemical Sciences, 2004. http://theses.library.uwa.edu.au/adt-WU2005.0017.
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This thesis is comprised of two parts. The first part describes the synthesis of cyclopentadienyltungsten complexes containing a pendant alkyne group (I), and the subsequent photo-induced intramolecular coordination of the alkyne, forming complexes such as II. Compounds containing intramolecularly coordinated alkynes are rare, and this is the first example using cyclopentadiene as the core ligand. The second part describes the synthesis and structural characterisation of a number of novel metal complexes containing N-heterocyclic carbene ligands, some containing particular functionality for taylored applications. New methods were used to form complexes of rhodium, iridium, silver and gold (eg. III, IV). Structural and spectroscopic properties of the complexes were correlated with electronic characteristics of the ancillary ligands. A number of rhodium and iridium complexes (eg. IV) derived from imidazolium-linked cyclophanes were synthesised and structurally characterised. Complexes of N-heterocyclic carbenes with pendant ionic groups were synthesised, and a preliminary examination of their catalytic activity in water was performed. N-Heterocyclic carbenes complexes containing an electron withdrawing nitro group were synthesised and the effect of the nitro group on metal-ligand bonding was examined.
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Eichler, Jack Frederick. "Coordination compounds possessing stannylamines synthesis, characterization and application /." Diss., Available online, Georgia Institute of Technology, 2004:, 2004. http://etd.gatech.edu/theses/available/etd-08242004-084134/unrestricted/eichler%5Fjack%5Ff%5F200412A%5Fphd.pdf.
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Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2005.William S. Rees, Jr., Committee Chair ; E. Kent Barefield, Committee Member ; Angus P. Wilkinson, Committee Member ; Z. John Zhang, Committee Member ; Dennis W. Hess, Committee Member. Includes bibliographical references.
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Le, Roux Adele. "Hard-hard and soft-soft coordination in complexes of Group 6 and Group 10 & 11 metals respectively." Thesis, Link to the online version, 2008. http://hdl.handle.net/10019/868.
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Wheaton, Craig Andrew. "The development of cationic zinc complexes as a new class of lactide polymerization catalyst." Thesis, Lethbridge, Alta. : University of Lethbridge, Dept. of Chemistry and Biochemistry, 2011, 2011. http://hdl.handle.net/10133/3108.
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The thesis outlines the development of novel cationic zinc complexes for application in lactide polymerization catalysis. These complexes were characterized spectroscopically and crystallographically, and where appropriate their efficacy as catalysts for the polymerization of lactide was evaluated.
The strongly donating, neutral chelating ligands employed in this study were prepared by installation of either one or two phosphinimine donors on a dibenzofuran backbone. An efficient synthetic methodology was then developed for the synthesis of cationic complexes of the formula [LZnE+][BAr4-], wherein E = C2H5, CH3, Ph, C6F5, OAc, OC6F5, or methyl-(D,L)-lactate, and AR = Ph, C6F5, or m-(CF3)2-C6H3. Only the cationic zinc-lactate species were found to be highly active polymerization catalysts.
Tuning of the steric and electronic properties of the ligand resulted in the discovery of zinc-lactate systems that promote rapid and well-controlled polymerization of lactide under mild conditions, marking the first well-defined cationic metal catalysts to do so.xxiv, 254 leaves : ill. ; 29 cm + 1 CD-ROM
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Chan, Wing-han. "Coordination chemistry of the pyridyl, naphthyridyl and [alpha], [omega]-polyether phosphine ligands and x-ray crystal structures and spectroscopic properties of the metal complex derivatives /." Hong Kong : University of Hong Kong, 1998. http://sunzi.lib.hku.hk/hkuto/record.jsp?B19481640.
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Hashiguchi, Ryota. "Studies on Polynuclear Metal Complexes and Low-Dimensional Mixed-Valence Halogen-Bridged Transition Metal Complexes Based on them." 京都大学 (Kyoto University), 2017. http://hdl.handle.net/2433/225426.
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Ng, Fei-yeung, and 吳飛洋. "Structure and properties of self-assembled coordination compounds: homoleptic d10-metal aryl/alkylacetylides, ruthenium n-heterocyclesand picolinates." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2006. http://hub.hku.hk/bib/B37878566.
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Chan, Wing-han, and 陳詠嫻. "Coordination chemistry of the pyridyl, naphthyridyl and [alpha], [omega]-polyether phosphine ligands and x-ray crystal structures andspectroscopic properties of the metal complex derivatives." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1998. http://hub.hku.hk/bib/B31236595.
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Ng, Fei-yeung. "Structure and properties of self-assembled coordination compounds : homoleptic d10-metal aryl/alkylacetylides, ruthenium n-heterocycles and picolinates." View the Table of Contents & Abstract, 2006. http://sunzi.lib.hku.hk/hkuto/record/B36587126.
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Sheng, Xia. "Competitive transport, extraction and coordination chemistry of a number of ligands with selected transition and post-transition metal ions." Thesis, Link to the online version, 2008. http://hdl.handle.net/10019/1488.
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De, Jongh Leigh-Anne. "Imine-donor complexes with group 6 and group 11 transition metals : coordination and dynamics." Thesis, Stellenbosch : Stellenbosch University, 2008. http://hdl.handle.net/10019.1/2001.
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Thesis (MSc (Chemistry and Polymer Science))--Stellenbosch University, 2008.In this study the coordination of ligands with several coordination sites, 2-aminoazoles (2- amino-4-methylthiazole), 2-aminobenzothiazole, 2-aminobenzoimidazole and 2- aminothiazoline and a biguanidine (N-(2-methylphenyl)imidodicarbonimidic diamide) to soft metal centres [gold(I) (group 11), chromium(0) (group 6) and tungsten (0) (group 6)] was investigated. The aminoazoles have three coordination sites, an exocyclic amine nitrogen, an endocyclic imine nitrogen and an endocyclic thioether sulphur. The biguanidine ligand has three sites for deprotonation, one central amine and two imine nitrogens, and at least five sites available for nitrogen coordination.
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Gallen, Ortiz Albert. "P-Stereogenic ligands with the tert-butylmethylphosphine fragment. Coordination chemistry and catalysis of their organometallic complexes." Doctoral thesis, Universitat de Barcelona, 2019. http://hdl.handle.net/10803/666577.
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The Thesis deals with the preparation, coordination chemistry and use in asymmetric homogeneous catalysis of several optically pure P-stereogenic ligands containing a tert-butylmethylphosphino fragment.
In the first part a highly stereoselective synthesis of the Secondary Phosphine Oxide (SPO) tert-butylmethylphosphine oxide is presented. Despite its simplicity, the stereoselective synthesis of this SPO had not been described in the literature. It is known that SPOs present a tautomeric equilibrium between the air-stable pentavalent form (phosphine oxide) and the trivalent form (phosphinous acid), usually completely shifted towards the pentavalent form but that can be displaced towards the phosphinous acid form by metal complexation. In the Thesis the complexation of the mentioned oxide towards Ru, Rh, Ir, Ni, Pd and Au has been explored, yielding a variety of coordination and organometallic compounds, with several coordination modes of the ligand. Some asymmetric catalytic applications of these species have also been studied, giving good conversions but low enantioselectivities.
In the second part of the Thesis, the C1-symmetric P-stereogenic ligand MaxPhos has been coordinated to [MCp*Cl] (M = Rh and Ir) and [Ru(p-cymene)Cl] fragments, yielding cationic M-stereogenic organometallic compounds as tetrafluoroborate or hexafluorophosphate salts. Interestingly, in all cases a single stereoisomer has been formed, as confirmed by NMR and X-ray crystallography. This has been rationalised by steric grounds. For Ir, the abstraction of the remaining chloride ligand by silver salts produced a diastereoselective C–H activation of a tert-butyl group of the ligand. The complexes have been used in transfer hydrogenation giving good activities but no enantioselectivities.
Finally the third part of the Thesis is devoted to the cyclometallation of [Ir(MaxPHOX)COD]BArF complexes (MaxPHOX stands for a type of P,N phosphinooxazoline ligand recently described by our group having three stereogenic centres) by several ligands under hydrogen atmosphere. It has been found that cyclometallated Ir(III)-hydrido complexes are formed, which are very stable and have been characterised thoroughly. They have been used in asymmetric hydrogenation of N-alkylimines, giving in general complete conversions and very high enantioselectivities (up to 96% ee) for these substrates, which rank among the best described to date. The mechanism of the reaction has been studied and the stereochemical outcome rationalised by means of DFT-based computational methods.La Tesi presenta la preparació, coordinació i ús en catàlisi homogènia asimètrica d’una varietat de lligands P-estereogènics òpticament purs que contenen el grup tert- butimetilfosfina. A la primera part es presenta la síntesi, altament estereoselectiva, de l’òxid de fosfina secundari (SPO) òxid de tert-butilmetilfosfina. Malgrat la simplicitat d’aquest compost, no se n’havia descrit la síntesi de forma estereoselectiva a la bibliografia. Se sap que els SPOs presenten un equilibri tautomèric entre la forma pentavalent estable a l’aire (òxid de fosfina) i la forma trivalent (àcid fosfinós). Habitualment aquest equilibri es troba totalment desplaçat envers la forma pentavalent però es pot desplaçar cap a l’àcid fosfinós per complexació amb un metall. A la Tesi, s’ha estudiat la complexació de l’òxid esmentat a Ru, Rh, Ir, Ni, Pd i Au i ha donat una gran varietat de compostos de coordinació i organometàl·lics, en els quals el lligand presenta una varietat de modes coordinació. També s’han explorat algunes aplicacions catalítiques d’aquestes espècies i s’han trobat bones conversions però baixes enantioselectivitats. A la segona part de la Tesi el lligand P-estereogènic de simetria C1 MaxPhos s’ha coordinat a fragments [MCp*Cl] (M = Rh o Ir) i [Ru(p-cimè)Cl] i ha donat compostos organometàl·lics catiònics M-estereogènics en forma de sals de tretrafluoroborat o hexafluorofosfat. És interessant destacar que estudis de RMN i cristal·lografia de raigs X han demostrat que en tots els casos s’ha format un sol estereoisòmer, fet que s’ha racionalitzat per arguments estèrics. En el cas del Ir, la abstracció del lligand cloruro amb sals de plata ha provocat l’activació de l’enllaç C–H d’un grup tert-butil de lligand en forma diastereoselectiva. Tots els compostos preparats s’han utilitzat en transferència d’hidrogen asimètrica i han donat bones activitats però enantioselectivitats baixes. Finalment, la tercera part de la Tesi està dedicada a la ciclometal·lació de complexos [Ir(MaxPHOX)COD)BArF amb diferents lligands auxiliars sota atmosfera d’hidrogen, on MaxPHOX és un lligand P,N de tipus fosfinooxazolina que el nostre grup de recerca ha descrit recentment i que conté tres centres estereogènics. S’ha observat la formació de complexos ciclometal·lats Ir(III)-hidrur molt estables, que s’han caracteritzat exhaustivament. Aquests complexos s’han usat com a catalitzadors per la reacció d’hidrogenació asimètrica d’imines alquíliques i ha donat conversions completes i enantioselectivitats de fins el 96% d’ee, que es troben entre els millors que s’han descrit mai per a aquests tipus de substrats. S’ha estudiat el mecanisme de la reacció i el curs estereoquímic, que s’ha racionalitzat mitjançant mètodes computacionals de tipus DFT.
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Calancea, Sergiu. "Synthèse et caractérisations de nouveaux complexes binucléaires à transfert d’électron de type {Fe(µ-CN)M} (M = Fe, Mn, Co)." Thesis, Bordeaux 1, 2013. http://www.theses.fr/2013BOR14802/document.
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L’une des grandes directions de recherche dans la chimie moderne est la synthèse et l’étude denouveaux composés « commutables » capables de modifier leurs propriétés sous l’effet de stimuli extérieurs (température, lumière, champ magnétique ou électrique…). Ces systèmes peuvent stocker une information à l’échelle moléculaire. Dans ce contexte, parmi les systèmes les plus étudiés en chimie de coordination figurent les réseaux et les analogues moléculaires du bleu de Prusse. Cette thèse est dédiée à la synthèse et aux caractérisations de nouveaux analogues moléculaires du bleu de Prusse à transfert d’électron de type {Fe(µ-CN)M} (M = Fe, Mn, Co). Dans le premier chapitre sont présentées les familles de composés commutables à transfert d’électron par ordre décroissant de leur dimensionnalité, des systèmes 3D vers des systèmes discrets 0D. Le deuxième chapitre regroupe la synthèse et les caractérisations structurales, spectroscopiques, magnétiques, et électrochimiques de complexes-précurseurs de type [MII(LN5)]2+ et [FeIII(LN3/LN2)(CN)n]- (n = 2, 3) (LN5, LN3, LN2 étantdes ligands azotés penta-, tri- ou bidentes, respectivement) qui seront ensuite utilisés dans la synthèse des composés binucléaires. Le troisième chapitre présente la synthèse et les études structurales,spectroscopiques, magnétiques, optiques et électrochimiques de quatre nouveaux composés binucléaires paramagnétiques {FeIII(µ-CN)MII} (MII = Fe, Co). Enfin, le quatrième chapitre se focalise sur la synthèse et les propriétés spectroscopiques, magnétiques, photomagnétiques et électrochimiques de trois nouveaux complexes binucléaires diamagnétiques {FeII(µ-CN)CoIII} à transfert d’électronOne of the main research directions of modern chemistry is the synthesis and study of new switchablecompounds which can change their properties under external stimuli (temperature, light, magnetic orelectric field…). These systems can store the information at the molecular level. In this contextamongst the most studied systems in coordination chemistry are the 3D networks and the molecularPrussian blue analogs. This thesis deals with the synthesis and characterizations of new{Fe(µ-CN)M} (M = Fe, Mn, Co) molecular Prussian blue analogs. In the first chapter electrontransfer compounds are described in order of decreasing of their dimensionality, from 3D to thediscrete 0D systems. The second chapter describes the synthesis and structural, spectroscopic,electrochemical and magnetic characterizations of [MII(LN5)]2+ precursors (MII = Fe, Mn, Co) and[FeIII(LN3/LN2)(CN)n]- (n = 2, 3) (LN5, LN3, LN2 - nitrogen-based penta-, tri- and bi-dentate ligands,respectively), which are used in the synthesis of the binuclear complexes. Chapter three presents thesynthesis and structural, magnetic, spectroscopic and electrochemical studies of four binuclearparamagnetic {FeIII(µ-CN)MII} complexes (MII = Fe, Co). Chapter four is focused on the synthesisand spectroscopic, magnetic, photomagnetic and electrochemical properties of three binucleardiamagnetic {FeII(µ-CN)CoIII} electron transfer complexes
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Gomes, de Lima Bernardes Miriam. "Réactivité de complexes organométalliques mono- et dinucléaires : synthèse de thiolato-composés du molybdène, du tungstène et du cobalt : étude de la formation de liaisons c-c dans la sphère de coordination du métal." Brest, 1986. http://www.theses.fr/1986BRES2008.
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Caracterisation des complexes ((c::(5)h::(5))(co)::(2) lwc(cf::(3)) = c(cf::(3))h) et (c::(5)h::(5))(co) lwc(o)c(cf::(3)) = c(cf::(3))h) (l=co,pr::(3),p(or)::(3)) synthese de complexes dinucleaires de mo et w. L'addition oxydante de dialkylsulfure a des derives biportes de mo(ii) et w(ii) a donne lieu a la formation de complexes thiolato triportes ((c::(5)h::(5))(co)m(mu -sr)::(3)m(co)(c::(5)h::(5)))tx**(-)
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Sishta, Chand. "The coordination chemistry of ruthenium porphyrin complexes." Thesis, University of British Columbia, 1990. http://hdl.handle.net/2429/30790.
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This thesis work reports developments in the coordination chemistry of ruthenium porphyrin complexes, both in terms of the synthesis and chemistry of new compounds, as well as the study of the solution chemistry of some previously reported complexes. The synthesis, characterization and chemistry of ten new Ru(porp) coordination complexes in the oxidation states Ru[superscript]Ⅲ and Ru[superscript]Ⅳ containing halide (Br, CI) and other axial ligands (pyridine, CH₃CN, NH₃ and SbF₆) are described in this thesis. Some additional ten Ru(porp) complexes have been studied in situ.
Measurement of the rate constants for forward and reverse reactions and the corresponding equilibrium constant by 'H NMR and UV/visible spectroscopy for the dissociation of PPh₃ ligand from Ru(OEP)L(PPh₃) (OEP is the octaethylporphyrinato dianion; L = CO, PPh₃) in C₇D₈ to generate the previously reported five-coordinate Ru(OEP)L complexes allowed for an estimation of the Ru-P bond strength (64 ± 9 kJ mol⁻¹) in these complexes. A study of PPh₃ dissociation from Ru(OEP)CO(PPh₃) in C₇D₈ and in CDC1₃ indicates that solvation effects play a major role, with CDC1₃ being more capable than C₇D₈ of solvating the Ru(OEP)CO complex. The presence of trace H₂0 in these systems was a major problem, and the coordination of H₂0 to Ru(OEP)L complexes to generate the in situ Ru(OEP)L(H₂0) complexes (L = CO, PPh₃) is described. The formation of Ru(OEP)L(H₂0) and the observed difference in the solvation of Ru(OEP)CO by C₇H₈ and CHC1₃ indicate that truly Five-coordinate species may not exist in solution. The outer-sphere oxidation of Ru [superscript]Ⅳ(OEP)PPh₃ by 0₂ to give [Ru [superscript]Ⅳ(OEP)OH]₂0 was shown to occur only in the presence of H₂0.
Mechanistic studies on the previously reported reaction of HCI with [Ru(OEP)]₂ to generate Ru^(OEP)Cl₂ (C. Sishta, M.Sc.Thesis, University of British Columbia, 1986) show that solvent plays a major role in directing this oxidation reaction. A reaction stoichiometry of 4:1 between HCI and [Ru(OEP)]₂ in C₆D₆ or C₇D₈ showed that HCI itself was the oxidant and not trace Cl₂ in HCI, as thought previously. A range of HX acids having pK[subscript]a, values in the range 38 to less than -10 (HX = H₂, MeOH, H₂0, H₂S, CH₃COOH, C₆H₅COOH, HF, CF₃COOH, HN0₃, HBF₄, HCI. HBr, and HSbF₆) were tested for reactivity with [Ru(OEP)]₂in C₆D₆; the data showed that a strong acid (pK[subscript]a < ca. 0) was necessary to initiate reactivity. The complex Ru[superscript]Ⅳ(OEP)(SbF₆)₂ was generated in situ by reacting HSbF₆ with [Ru(OEP)]₂.
In CH₂C1₂, a 1:1 stoichiometric reaction between HCI and [Ru(OEP)]₂ was observed, instantly fanning a mixture of products, tentatively formulated as Rura(OEP)H and [Ru[superscript]Ⅲ(OEP)]₂CHCl₂ based on spectroscopic data. The species proved impossible to separate. These same products were formed slowly by the reaction of [Ru(OEP)]₂ with CH₂C1₂ in the absence of HCI, and kinetic studies suggest that a direct reaction of [Ru(OEP)]₂ with CH₂C1₂ is likely, rather than reaction of [Ru(OEP)]₂ with impurities in CH₂C1₂. The product mixture generated Ru(OEP)Cl₂ upon further reaction with HCI, both in the absence and in the presence of air. The complex Ru[superscript]Ⅳ(OEP)(BF₄)₂ was generated in situ by an analogous reaction of aqueous HBF₄ with the product mixture. The required hydrogen-containing co-product from the reaction of HX (X = Br, CI) with [Ru(OEP)|₂ in C₇D₈ or CH₂C1₂ was not detected, but was shown not to be H₂.
Oxidation of Ru(porp)(CH₃CN)₂ and Ru(OEP)py₂ (py = pyridine; porp = OEP, TMP (the dianion of tetramesitylporphyrin)) by gaseous HX (X = Br, CI) in the absence of air yielded Ru[superscript]Ⅳ(porp)X₂ complexes. The new compound Ru(TMP)Br₂ was synthesized by this method using the bis(acetonitrile) precursor, and was characterized by spectroscopy; the chloride analogue Ru(TMP)Cl₂ was generated in situ.
The magnetic properties (susceptibility and moment) of Ru(OEP)Br₂ from 6 to 300 K are unlike those reported for ruthenium(IV) non-porphyrin complexes, and reveal a significant contribution from temperature-independent paramagnetism.
The reaction of Ru(OEP)X₂ (X = Br, CI) with NH₃ gave the complexes Ru[superscript]Ⅲ(OEP)X(NH₃), which upon acidification under an inert atmosphere yielded the Rum(OEP)X compounds. These Ru111 complexes were characterized by spectroscopic techniques, and the solution chemistry of the five-coordinate species Ru(OEP)X was developed: the Ru[superscript]Ⅲ(OEP)X(CH₃CN) species were also characterized. Solvation of the five-coordinate species Ru(OEP)X (X = Br, CI) was observed in coordinating solvents to form the six-coordinate species Ru(OEP)X(solvent) (solvent = py, CH₃CN and MeOH). Estimates of the equilibrium constants for the association of these ligands to Ru(OEP)X were obtained from UV/visible titration experiments in CH₂C1₂. Similarly, the equilibrium constant for the association of Br to Ru(OEP)Br to generate in situ (n-Bu)₄N⁺[Ru[superscript]Ⅲ(OEP)Br⁺₂]", was measured. Disappointingly, the complexes Ru(OEP)X were shown not to catalyze the oxidation of organic substrates such as cyclohexene.
Electrochemical and spectroelectrochemical studies of the complexes Ru(OEP)X₂ and Ru(OEP)X (X = Br, CI) showed that the Ru[superscript]Ⅳ/Ru[superscript]Ⅲ couple occurred at 480-460 mV and 950-870 mV vs. NHE, respectively, and that the probable reductant for the reaction of Ru(OEP)X₂ with NH₃ was NH₃ itself. A facile reduction of Ru(OEP)(SbF₆)₂ gave the complex Ru[superscript]Ⅲ(OEP)SbF₆, by a probable homolysis of the Ru-F bond.
The outer-sphere oxidation of Ru(OEP)py₂ by air in the presence of HX acids gave the isolated or in situ characterized complexes [Ruin(OEP)py₂]+ X" (X = CI, Br, F, BF₄). Similar oxidation of Ru(OEP)(CH₃CN)₂ formed [Ru(OEP)(CH₃CN)₂]+ Br-. Electrochenucal studies showed that 0₂ in acidic media was capable of oxidizing the Ru(OEP)(solvent)₂ complexes (solvent = py, CH₃CN) to the Ru[superscript]Ⅲ complexes, presumably generating H0₂ .Science, Faculty of
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Mobbs, B. E. "Arene transition metal complexes in synthesis." Thesis, University of Oxford, 1985. http://ora.ox.ac.uk/objects/uuid:4c7030d4-297e-4af8-a622-d5b4963fc0a3.
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This thesis deals with the applications of organopalladium and organochromium chemistry to the functionalisation of the benzopyran ring system, at a variety of oxidation levels. Section I demonstrates the functionalisation of 3-, 6-, and 8-bromochromones via palladium (0) insertion into the C-Br bond. The resultant arylpalladium species are shown to undergo addition to the least substituted end of a variety of olefins including methyl acrylate, acrylonitrile and styrene. Subsequent palladium-hydride elimination leads to overall palladium catalysed vinylation of the chromone and the synthesis of a number of novel compounds. Vinylation occurs regiospecifically at the site of chromone bromination and is shown to allow clean substituent introduction into each of the three sites. The palladium catalysed reaction of 3,6-dibromo-chromone with methyl acrylate leads to vinylation at both the C3 and C6 positions. Carbonylation of the 6-bromochromone in ethanol or butanol leads to the 6-ethyl or 6-butyl esters respectively. The palladium catalysed vinylation of the 6-bromochromone with ethyl vinyl ether leads to a mixture of products from addition of the chromone to either end of the olefin. With p-bromophenol or p-bromo-N,N-dimethylaniline the reaction gives exclusively the acetylated product arising from addition to the more substituted end of the olefin. This change in orientation is rationalised by considering the polarisation of the olefin and the arylpalladium species. Section II demonstrates the functionalisation of chroman and 4-chromanol via coordination to the Cr(CO)3 moiety. (η6-Chroman)Cr(CO)3 is synthesised and is shown to undergo regiospecific ring deprotonation at C8 under kinetic conditions or regiospecific benzylic deprotonation at C4 under thermodynamic conditions. The resultant anions are quenched with alkyl halides, aldehydes, Eschenmoser's salt and methyl disulphide resulting in selective functionalisation of either site. No mixed products are observed. The uncomplexed arene is shown to be totally unreactive under identical conditions. (η6-4-Chromanol)Cr(CO)3 is synthesised and is shown to undergo regiospecific C8 ring deprotonation by comparison with authentic samples of the C5 and C8 methylated alcohols. Protection of the hydroxyl group as its methyl, t-butyldimethylsilyl or methoxymethyl ethers is found not to alter the regiochemistry of deprotonation. The 4-chromanol t-butyldimethylsilyl and tri-i-propylsilyl ethers are synthesised and coordinated to the metal unit. Cleavage of the silyl ethers is shown to proceed with loss of stereochemistry, indicating C-0 bond cleavage.
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Carter, Timothy Glen 1976. "New supramolecular assemblies of toxic metal coordination complexes." Thesis, University of Oregon, 2010. http://hdl.handle.net/1794/10562.
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xvii, 147 p. : ill. (some col.) A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number.Supramolecular chemistry is a relatively new and exciting field offering chemists simplistic approaches to generating complex assemblies through strategically designed ligands. Much like the many spectacular examples of supramolecular assemblies in nature, so too are chemists able to construct large, elegant assemblies with carefully designed ligands which bind preferentially to target metal ions of choice. An important concept of supramolecular chemistry, often subtle and overlooked, is secondary bonding interactions (SBIs) which in some cases, act as the glue to hold supramolecular assemblies together. This dissertation examines SBIs in a number of systems involving the pnictogen elements of arsenic and antimony as well as aromatic interactions in self-assembled monolayers. The first half of this dissertation is an introduction to the concepts of supramolecular chemistry and secondary bonding interactions and how they are used in the self-assembly process in the Darren Johnson laboratory. Chapter I describes how secondary bonding interactions between arsenic and aryl ring systems and antimony and aryl ring systems assist with the assembly process. Chapter II is a continuation of the discussion of SBIs but focuses on the interactions between arsenic and heteroatoms. The second half of this dissertation will describe work performed in collaboration with Pacific Northwest National Laboratory (PNNL) in Richland, WA. This work was performed under the guidance of Dr. R. Shane Addleman in conjunction with Professor Darren W. Johnson of the University of Oregon. This portion describes novel systems for use in heavy metal ion remediation from natural and unnatural water sources. Chapters III-V describe functionalized mesoporous silica for use in heavy metal uptake from contaminated water sources. Chapter V describes a new technology invented during this internship at PNNL which utilizes weak bonding interactions between aryl ring systems to produce regenerable green materials for toxic metal binding. This work is ongoing in the Darren Johnson lab. This dissertation includes my previously published and co-authored material.
Committee in charge: Michael Haley, Chairperson, Chemistry; Darren Johnson, Member, Chemistry; Shih-Yuan Liu, Member, Chemistry; James Hutchison, Member, Chemistry; Eric Johnson, Outside Member, Biology
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Smith, Alexis. "Coordination complexes of trivalent non-transition metal ions." Thesis, University of British Columbia, 1988. http://hdl.handle.net/2429/28400.
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Lathaxride(III) complexes of three potentially heptadentate Schiff base ligands were prepared by addition of lanthanide(III) salts to a solution containing a slight excess of ligand in the presence of poorly coordinating chloride ions or strongly coordinating nitrate ions. The complexes La(hatren), La(datren)(CH₃0H) and La(trac) were isolated in the presence of chloride ions, and were found to have the ligand bound in a hexadentate or heptadentate fashion. We were unable to isolate analogous complexes with the heavier lanthanides (Ln = Pr, Nd, Gd, Dy, Yb, Lu). The complexes Ln(H₃L)(NO₃)₃ (Ln = La, Pr, Nd, Gd, Dy, Yb; H₃L =
H₃hatren, H₃datren) and Ln(H₃trac)(NO₃)₃ (Ln = Pr, Nd, Gd, Dy, Yb) were isolated in the presence of nitrate ions, and were found to have the Schiff base ligand bound in a tridentate fashion ( where H₃datren = tris(2'-hydroxy-4',5'-dimethylacetopheniminoethyl)amine; H₃trac = tris(3-aza-4-methylhept-4-ene-6-one)amine; and H₃hatren = tris(2'-hydroxyacetophenirninoethyl)amine)
All products were characterized by infrared and mass spectroscopy, and by elemental analysis. ¹H-NMR spectroscopy indicated that the complexes were solution labile and dissociated in DMSO to yield free ligand and solvated lanthanide(III) ions.
The crystal structure of Gd(H₃trac)(NO₃)₃ was determined. The gadolinium(III) ion is nine coordinate. H₃trac is bound only through its three oxygen donor atoms, and the nitrate ions are bound in a bidentate fashion to the gadolinium center.
Aluminum (III) and gallium(III) complexes of 2-chloromethyl-5-hydroxy-4H-pyran-4-one (Hck) were isolated from a basic aqueous solution. The complexes Al(ck)₃ and Ga(ck)₃ were characterized by ¹H-NMR (CDCI₃), infrared and mass spectroscopy, as well as by elemental analysis. Al(ck)₃ was also characterized by ²⁷Al-NMR in CDCI₃.Science, Faculty of
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Cetin, Anil. "TRANSITION METAL COMPLEXES OF PORPHYRIN ANALOGS AND BORATE-BASED COORDINATION COMPLEXES." University of Akron / OhioLINK, 2007. http://rave.ohiolink.edu/etdc/view?acc_num=akron1176390111.
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DuPont, Julie A. "The coordination chemistry of thioether-supported, low-valent cobalt complexes." Access to citation, abstract and download form provided by ProQuest Information and Learning Company; downloadable PDF file 3.92 Mb., 165 p, 2006. http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&res_dat=xri:pqdiss&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&rft_dat=xri:pqdiss:3200521.
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Kurawa, Mukhtar Atiku. "Solid State Sythesis of Metal Salts and Coordination Compounds." Thesis, University of Bristol, 2009. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.503896.
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Wambach, Truman C. "Cooperative ligand design for late transition metal coordination compounds." Thesis, University of British Columbia, 2015. http://hdl.handle.net/2429/52014.
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This thesis describes several cyclopentyl linked enamide phosphine ligands. Reactivity and mechanistic studies using coordination compounds featuring these ligands enable exploration of ligand cooperativity.
Despite complex behavior in solution due to tautomerization, coordination of (NPN)DMP/DIPPH₂ to Rh generates RhCl{(NPN)DMP/DIPPH₂}(COE). Synthesis of RhCl{(NPN)DMP/DIPPH₂}(CO) and RhHCl₂{(NPN)DMP/DIPPH₂} is possible. NMR spectroscopy and in certain cases X-ray analysis establishes the diimine tautomer of the ligand coordinates to Rh in each case.
Enamide phosphine complexes, Ir{(NP)DIPP}(COD) and Ir{(NP)DMP}(COD) are synthesized from simple imine phosphine ligands. Ir{(NP)DIPP}(COD) reacts with H₂ or PriOH to form [IrH₃{(NP)DIPPH}]₂. The imine tautomer of the ligand coordinates to Ir. Treating [IrH₃{(NP)DIPPH}]₂ with CO generates Ir{(NP)DIPP}(CO)₂. A proton from the imine ligand of [IrH₃{(NP)DIPPH}]₂ combines with an Ir hydride to release H₂. Observation of three intermediates, involved in conversion of [IrH₃{(NP)DIPPH}]₂ to Ir{(NP)DIPP}(CO)₂, suggests that tautomerization of the dissociated arm is involved in cooperative H₂ loss.
Four imine phosphine ligands (R(NP)R'H), where the N-aryl groups (R) and the groups attached to P(R') are varied, are synthesized. Combining each ligand with RuHCl(PPri₃)₂(CO) and KOBut generates four enamide phosphine complexes: RuH{R(NP)R'}(PPri₃)(CO). Reacting RuH{R(NP)R'}(PPri₃)(CO) with H₂ generates RuH₂{R(NP)R'H}(PPri₃)(CO). The imine tautomeric form of the ligand coordinates to Ru in all four cases. The R' groups influence the rate of reaction and percent conversion to RuH₂{R(NP)R'H}(PPri₃)(CO). The mechanism for H₂ activation is explored using RuH{Pri(NP)Pri}(PPri₃)(CO). An intermediate is identified as RuH₂(H₂){Pri(NP)PriH}(PPri₃)(CO). The T₁,min value of a ¹H NMR resonance at δ -7.2 is 22 ms at 238 K (measured to 400 MHz), consistent with a Ru dihydrogen dihydride complex. The N donor of the enamine tautomeric form of the ligand is protonated by H₂ or D₂ and has dissociated from Ru. Tautomerization of the dissociated arm is involved in formation of the final product.
Certain factors inhibit alcohol dehydrogenation catalysis for Ir{(NP)DIPP}(COD) and RuH{Pri(NP)Pri}(PPri₃)(CO). Two tridentate enamide phosphine ligands are developed in an effort to generate a catalyst. These ligands enable synthesis of RuH{(PNN)But}(CO) and RuH{(PNN)Pri}(CO). Exposing RuH{(PNN)But}(CO) to 1000 equivalents of benzyl alcohol yields a TON of 13 and TOF of 0.6 h-¹ after 22 hours. Nearly identical results are obtained for RuH{(PNN)Pri}(CO).Science, Faculty of
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Humphrey, Paul Andrew. "A study of transition metal complexes /." Title page, contents and summary only, 1990. http://web4.library.adelaide.edu.au/theses/09PH/09phh9262.pdf.
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Yu, Pui-yin. "Metal alkylidyne complexes as building blocks for molecular materials /." Hong Kong : University of Hong Kong, 1998. http://sunzi.lib.hku.hk/hkuto/record.jsp?B19470514.
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Schulte, Thorben Rüdiger. "Metal- and Ligand-Centered Chirality in Square-Planar Coordination Compounds." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2018. http://hdl.handle.net/21.11130/00-1735-0000-0005-126A-0.
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Wilson, Paul John. "Early transition metal imido complexes supported by heterocyclic ligands." Thesis, University of Nottingham, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.285593.
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Jones, Simon C. "Metal-metal coupling in bi- and multimetallic systems : organometallic pentalene and group 14-bridged cyclopentadienyl complexes of transition metals." Thesis, University of Oxford, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.270635.
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Chiu, Winnie Wai Hang. "Metal complexes with sulfur and selenium donor ligands /." View abstract or full-text, 2009. http://library.ust.hk/cgi/db/thesis.pl?CHEM%202009%20CHIU.
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Partridge, Martin Graham. "Activation and coordination of organic ligands by cyclopentadienyl metal complexes." Thesis, University of York, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.304072.
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O'Connor, Alice. "High pressure studies of metal-organic frameworks and coordination complexes." Thesis, University of Nottingham, 2017. http://eprints.nottingham.ac.uk/40333/.
Full textAbstract:
High pressure X-ray crystallography is an effective tool for studying the behaviour of systems in the solid state. It is becoming an increasingly popular technique and offers a way to determine and monitor the behaviour of systems, which in some cases is necessary in order for those particular materials to be used in real-world applications. This thesis explores the use of high pressure X-ray crystallography to understand the behaviour of systems such as metal-organic frameworks (Chapters 4and 5) and the coordination complexes, [1,4-C6H4{PPh2(AuCl)}2](Chapter 6) and chloro(4-ethoxycarbonyl-6-phenyl-2,2′-bipyridyl)platinum (Chapter 7). It also describes hydrostatic limit determinations carried out on 4:1 MeOH/EtOH with additional additives such as silicon grease and/or crystals of [PdCl2([9]aneS2O)] to see how the hydrostatic limit might be manipulated by the use of these additives. It has been possible to determine the hydrostatic limit of a possible pressure-transmitting medium, namely RS3000, which showed an increased pressure limit when compared to the hydrostatic limits for other similar media. This thesis therefore covers a wide range of studieshighlighting some of the diversity that this fieldoffers. To betterunderstand the behaviour of the systems studied, several ancillary techniques have been employed including Hirshfeld surface analysis, Raman spectroscopy, UV/visible spectroscopy and theoretical calculations. In all cases these techniques provided useful information which complemented the results of the high pressure X-ray crystallographic studies.
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Chan, Hoi-shan. "Syntheses, reactivity and coordination chemistry of d10 metal complexes of phosphorus and nitrogen donating polydentate ligands /." Hong Kong : University of Hong Kong, 1999. http://sunzi.lib.hku.hk/hkuto/record.jsp?B2079289X.
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Reeves, GorDan T. Addison Anthony W. "Ruthenium(II) complexes of multidentate thioether and amine ligands /." Philadelphia, Pa. : Drexel University, 2009. http://hdl.handle.net/1860/3000.
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Meade, Thomas Joseph. "Inclusion complexes of molecular transition metal hosts /." The Ohio State University, 1985. http://rave.ohiolink.edu/etdc/view?acc_num=osu1487262513406675.
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Banham, Andrea Kaye. "Stereoselective functionalization of acyclic organoiron complexes." Thesis, University of East Anglia, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.241477.
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俞佩賢 and Pui-yin Yu. "Metal alkylidyne complexes as building blocks for molecular materials." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1998. http://hub.hku.hk/bib/B31238002.
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Lam, Chan-fung. "Synthesis, optical and luminescence studies of rhenium(I) diimine alkynyl complexes and their utilization as building blocks for the assembly of multinuclear and mixed-metal complexes." Click to view the E-thesis via HKUTO, 2005. http://sunzi.lib.hku.hk/hkuto/record/B32010564.
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Parrott, Suzanne J. "The coordination chemistry of hydrazide and diazenide complexes of rhenium." Thesis, University of Essex, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.315728.
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Fleming, James S. "d'8-metal complexes of 1,8-divinylnaphthalene and 1,2-divinylbenzene." Thesis, University of Bristol, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.385969.
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McQuaid, Michael James. "Spectroscopic characterization of metal-based complexes and metal-based complex oxidation processes." Diss., Georgia Institute of Technology, 1989. http://hdl.handle.net/1853/30334.
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Atkinson, Nigel Anthony. "Transition metal complexes with sulphur/nitrogen donor macrocycles and related ligands." Thesis, University of Huddersfield, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.290395.
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Blincko, Stuart. "Novel luminescent compounds for immunoassay." Thesis, City University London, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.255249.
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Kaur, Gurpreet. "Structure and reactivity of dinuclear and polynuclear metal complexes." Thesis, University of Canterbury. Chemistry, 2014. http://hdl.handle.net/10092/9945.
Full textAbstract:
This thesis documents the successful syntheses of six novel 2,2':6',2"-terpyridine-amine based polydentate ligands and a range of mono-, di-, and polynuclear complexes derived from them. The ability of some dinuclear complexes to affect the rate of hydrolysis of the phosphate diester group in the DNA model compound, bis-p-nitrophenyl phosphate (BNPP) has also been explored. Owing to the presence of two potential ligating groups in each polydentate ligand, a number of dinuclear, tetranuclear and serendipitous supramolecular architectures have been produced and characterised during this research.
The polydentate ligands were synthesised by stepwise functionalisation of the progenitor ligand, 4'-(2"'-toluyl)-2,2':6',2"-terpyridine (L2.1), at its ortho methyl position via free radical bromination, and where various amine groups were appended by nucleophilic substitution reactions. The detailed ligand syntheses, and characterisation are discussed in Chapter 2, along with the crystal structures of some ligands.
Chapter 3 describes coordination chemistry of 4'-(2"'-toluyl)-2,2':6',2"-terpyridine with transition metal ions. Thirteen new complexes of Ni(II), Cu(II), Zn(II) and Ag(I) are reported, where Ag(I) produced a striking spiral shaped polymer with L2.1 having unusual „hyperdentate‟ nitrogen atoms.
Two polydentate ligands, 4'-[2"'-{(2-pyridylmethyl)aminomethyl}phenyl]-2,2':6',2"-terpyridine, L2.3, and 4'-[2"'-{bis(2-pyridylmethyl)aminomethyl}phenyl]-2,2':6',2"-terpyridine, L2.4, produced six different dinuclear and tetranuclear metal complexes (Chapter 4).
The Zn(II) dinuclear complexes were used to study kinetics of hydrolysis of BNPP, and the enhanced rates were reported compared to the analogous mononuclear complexes. The detailed experimental methodology and results are discussed in Chapter 5.
The most interesting outcome of this research was formation of the box and wheel shaped complexes, where the ligand L2.3 binds with different metal ions via different coordination modes. The box shaped tetranuclear complexes were synthesised deliberately via structural control over the coordination chemistry of terpyridine-type site of L2.3, where the coordination flexibility of the pendent picolylamine-type site of the ligand was used to bind with other metal ions.
The tetranuclear [M¹₂M²₂(L2.3)₄X₂]⁶⁺ box shaped complexes were formed when two divalent M¹ ions bridge between the ligands to produce octahedral bis-terpyridine type complex M¹(L2.3)₂, and then two divalent M² ions link two M¹(L2.3)₂ units together through picolylamine binding sites, where X = Cl⁻, Br⁻, CH₃COO⁻; M¹ = Fe(II), Zn(II), Ni(II); M² = Zn(II), Cu(II).
The bis-bidentate bridging ligand terephthalate was also deliberately encapsulated in the middle of Fe₂Zn₂L2.3 box to produce the complex where X₂ = terephthalate. These structures invite speculation that it may be possible to bind and react molecules within these boxes.
In a more fortuitous outcome, Ni(II) ions were found to bind to both sites of L2.3 to give, exclusively, an unprecedented decanuclear wheel-shaped structure. A halide ion occupies the central position in the wheel, with Br⁻ being preferred over Cl⁻. The detailed crystal structures, and properties of the wheels shaped Ni₁₀(L2.3)₁₀ complexes are discussed in Chapter 6.
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Sinha, Pankaj Omary Mohammad A. "Phosphorescent emissions of coinage metal-phosphine complexes theory and photophysics /." [Denton, Tex.] : University of North Texas, 2009. http://digital.library.unt.edu/ark:/67531/metadc12200.
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