Dissertations / Theses: 'Metal complexes Metal complexes Ligands'

1

Cheung, Wai Man. "Transition metal complexes with dichalcogenoimidodiphosphinate ligands /." View abstract or full-text, 2007. http://library.ust.hk/cgi/db/thesis.pl?CHEM%202007%20CHEUNG.

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2

McHugh, Paul. "Oligonuclear metal complexes of compartmental ligands." Thesis, University of Sheffield, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.408313.

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3

Onyiriuka, Emmanuel C. "Pyrazolyl ligands in mixed metal complexes." Thesis, University of British Columbia, 1986. http://hdl.handle.net/2429/27178.

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The anions LMo(CO)₃⁻ (L = MeGapz₃ or MeGa(3,5-Me₂pz)₃) have been isolated as the Na⁺, Et₄N⁺ or HAsPh₃⁺ salts and the solution structures of the Na⁺ salts in THF have been defined by analysis of the v[sub CO] ir spectra. Ion-pair interaction of the LMo(CO)₃⁻ anion with Na⁺cation in THF solution is apparent from the spectroscopic evidence obtained. The MeGapz₃Mo(CO)₃ ⁻anion reacted with HCl or EtBr to give the seven-coordinate [MeGapz₃]-Mo(CO)₃R (R = H or Et) complexes. However, with Mel or PhCOCl complexes of the type [MeGapz₃]Mo(CO)₂(n₂-COR) (R = Me or Ph) were obtained. The reactions of the LMo(CO)₃⁻ ions (L = MeGapz₃ HBpz₃ or Me₂Gapz(0-CH₂CH₂NMe₂)) with a variety of transition metal halide species have yielded complexes with transition metal-transition metal bonds. The X-ray crystal structures of two such complexes [MeGapz₃]Mo(CO)₃Cu(PPh₃) and [MeGapz₃]Mo-(CO)₃Rh(PPh₃)₂ have been determined. The former complex provides a rare example of a 3:3:1, or capped octahedral structure, with a short (mean) Mo-Cu distance of 2.513(9)Å. The latter compound displays one terminal and two bridging CO ligands and a Mo-Rh distance of 2.6066(5)Å. Transition metal-group 14 (Si, Ge or Sn) element bonded complexes of the type [MeGapz₃]Mo(CO) ₃M'Y (Y = Me₃ or Ph₃, M' = Ge or Sn; Y = Me₃, M' = Si; Y = Me₂Cl, M' = Sn) have been prepared from the reaction of the MeGapz₃Mo(CO)₃anion with the appropriate organo-group 14 chloride. In all the complexes, direct Mo-M' (M' = Si, Ge or Sn) single bonds are featured. The [MeGapz₃]Mo(CO) ₃SnMe₂Cl complex shows an interesting solution behaviour in which a transition from a 3:4, or piano stool structure, to a 3:3:1, or capped octahedral arrangement, is thought to occur. The 3:3:1 structure has been demonstrated in the solid state for the [MeGapz₃]Mo(CO)₃SnPh₃ compound by means of a crystal structure determination. The 'Mo-SnPh₃' and the 'Mo-Cu' compounds discussed in this work are the first examples of such complexes incorporating either the MeGapz₃⁻, HBpz₃⁻ or C₅H₅⁻ ligands in which the 3:3:1 arrangement has been demonstrated unequivocally. The novel tridentate unsymmetric ligands Me₂GapzO(C₅H₃N)CH₂NMe₂⁻ (L[sub a]⁻) and Me₂GapzO(C₉H₆N)⁻ (L[sub q]⁻) have been prepared and numerous transition metal compounds containing these ligands synthesized. The compounds L[sub a] M(CO)₃(M = Mn or Re) are the first examples of transition metal carbonyl complexes in which both the fac and mer arrangements of the unsymmetric ligand about the central metal have been found to co-exist in solution. The square planar rhodium(I) complex, L[sub q]Rh(CO) has been shown to add Mel oxidatively, followed by facile methyl migration reaction to produce the five-coordinate Rh(III) acetyl derivative, L[sub q]Rh(COMe)I. In contrast, the reaction of L[sub a]Rh(CO) with Mel, led to the six-coordinate Rh(III) oxidative addition product, L[sub a]Rh(Me)(I)CO.
Science, Faculty of
Chemistry, Department of
Graduate

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4

Crofts, Rhona D. "Platinum metal complexes of macrocyclic ligands." Thesis, University of Edinburgh, 1995. http://hdl.handle.net/1842/13493.

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5

Humphrey, Elizabeth Rebecca. "Tris(pyrazolyl)borate metal complexes : new ligands and metal-metal interactions." Thesis, University of Bristol, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.340301.

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6

Ho, Kin-ying. "Synthesis, characterization and spectroscopic properties of d6 and d10 metal complexes with pyridyl amine ligands /." Hong Kong : University of Hong Kong, 1999. http://sunzi.lib.hku.hk/hkuto/record.jsp?B20667905.

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7

Stewart, Peter John. "Metal-ligand multiply bonded complexes supported by amidinate ligands." Thesis, University of Nottingham, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.243747.

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8

Dubberley, Stuart R. "New calix[4]arene metal complexes." Thesis, University of Oxford, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.365290.

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9

Lam, Chong Ho. "Metal complexes containing oxygen tripod ligands : models of metal oxides /." View Abstract or Full-Text, 2003. http://library.ust.hk/cgi/db/thesis.pl?CHEM%202003%20LAMC.

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Thesis (Ph. D.)--Hong Kong University of Science and Technology, 2003.
Includes bibliographical references (leaves 275-290). Also available in electronic version. Access restricted to campus users.

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10

Landman, Marile. "Synthesis of metal complexes with thiophene ligands." Thesis, Access to E-Thesis, 2000. http://upetd.up.ac.za/thesis/available/etd-12042006-143722/.

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11

Graham, Todd Warren. "Mixed-metal complexes incorporating polydentate bridging ligands." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape7/PQDD_0028/NQ39533.pdf.

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12

Skinner, Michael E. G. "Transition metal complexes of diamide-diamine ligands." Thesis, University of Oxford, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.365390.

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13

Niven, Stuart. "Chelating carbene ligands and their metal complexes." Thesis, Cardiff University, 2007. http://orca.cf.ac.uk/54628/.

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This thesis describes the synthesis of a number of functionalised imidazolium salts as precursors to N- heterocyclic carbenes and their subsequent coordination to Ag and Pd. Further a number of the Pd complexes were tested in the Heck reaction and their activities compared to complexes with similar structural features currently within the literature. A range of imidazolium salts have been synthesised which include quinoline and octahydroacridine moieties and have been characterised by a number of methods including X-ray crystallography. A bis imidazolium salt has also been prepared as a DIOP analogue. The imidazolium salts were successfully reacted with Ag20 to form the NHCAg(I) complexes. The quinoline and octahydroacridine based NHCs were transmetallated to Pd as chelating ligands, the quinoline based systems appearing as planar, strained complexes in the X-ray structure. The activities of the quinoline and octahydroacridine based NHCPd(II) complexes in the Heck coupling of 4-bromoacetophenone and 4-chlorobenzaldehyde with n-butyl acrylate were assessed and found to be comparable to similar systems with low to satisfactory conversions.

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14

O'Shaughnessy, Paul. "Alkali metal complexes of phosphorus donor ligands." Thesis, University of Newcastle Upon Tyne, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.323668.

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15

Okey, J. N. "Metal complexes of nitrogen-donor heteroaromatic ligands." Thesis, Imperial College London, 1987. http://hdl.handle.net/10044/1/47492.

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16

Seidel, Scott William 1971. "Transition metal complexes containing chelating amido ligands." Thesis, Massachusetts Institute of Technology, 1998. http://hdl.handle.net/1721.1/47411.

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17

Olson, Michael David. "Pyrazolyl based ligands in transition metal complexes." Thesis, University of British Columbia, 1989. http://hdl.handle.net/2429/27610.

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Several uninegative/ multidentate pyrazolyl based ligands were synthesized [eg. HBPZ₃₋, HBpz”₃₋, MeGapz₃₋/ MeGapz” ₃₋, H2BpZ₂₋/ Me2Bpz₂₋/ Me2GapZ₂₋/ Me2Gapz"₂₋/ Me₂Gapz(OCH₂CH₂NH₂)⁻Me₂Gapz(OCH₂CH₂CH=CH₂)⁻ ; pz pyrazolyl/ pz" = 3, 5 dimethylpyrazolyl]. These ligands were reacted with the sterically hindered metal complex, HBpz*₃MCl (M = Co, Ni; pz* = 3-iPr-4-Br-pyrazolyl) and the mixed-ligand transition metal complexes of general formulae, HBpz*₃ML, were isolated. The X-ray crystal structure of one such complex, HBpz*₃Nipz"₃BH was determined showing a near octahedral arrangement of ligands about the nickel centre. The electronic spectra of the nickel complexes were recorded and compared to predicted transitions. The electronic spectra of the four coordinate nickel complex, HBpz*₃NiCl, fit a d⁸, tetrahedral, ligand field model. The six coordinate complexes, HBpz*₃NiL (L = HBPZ₃, HBpz"₃, MeGapz₃, MeGapz”₃), fit a d⁸, octahedral, ligand field model. The unsymmetrical pyrazolylgallate ligands were reacted with the rhodium dimer [Rh(CO)₂CI]₂ to give the square planar complexes, LRh(CO) [L = Me2Gapz(OCH₂CH₂NH₂), Me₂Gapz(OCH₂CH₂CH=CH₂)]. These rhodium[I] complexes appeared to undergo oxidative additions of Mel, allylbromide and I₂. Furthermore these rhodium[I] complexes appeared to bind the small gas molecules, CO and ethene. A number of heterobimetallic complexes, with direct metal-metal bonds, were prepared and isolated from the reaction of the molybdenum anion, HBpz"₃(CO)₃MO⁻ with the transition metal halides, [CuPPb₃Cl]₄, SnR₃Cl (R = Me, Ph) and GePh₃Cl.
Science, Faculty of
Chemistry, Department of
Graduate

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18

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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19

何建英 and Kin-ying Ho. "Synthesis, characterization and spectroscopic properties of d6 and d10metal complexes with pyridyl amine ligands." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1999. http://hub.hku.hk/bib/B31220885.

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20

Zhang, Lilu. "Synthesis and chemistry of lanthanide complexes with phosphorus ylides, amides or porphyrinate ligands, and of transition metal complexes with polydentate ligands." HKBU Institutional Repository, 1999. http://repository.hkbu.edu.hk/etd_ra/182.

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21

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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22

Khandelwal, B. "Metal complexes of electron-rich arsenic-sulphur ligands." Thesis, University of Exeter, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.378245.

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23

Bell, Michael Niall. "Organometallic platinum group metal complexes incorporating macrocyclic ligands." Thesis, University of Edinburgh, 1987. http://hdl.handle.net/1842/13895.

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24

Burgess, Michael Graeme. "Metal Complexes of Acyclic and Macrocyclic Multifunctional Ligands." Thesis, University of Auckland, 2008. http://hdl.handle.net/2292/5171.

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This thesis describes the design, synthesis and study of metal derivatives of new acyclic and macrocyclic ligands containing pyridine and amide groups. Chapter 1 provides an overview of metal-carboxamide and pyridinamide chemistry including a number of important pincer compounds, macrocyclic involvement in formation of metal-templated rotaxanes and catenanes, oxidation catalysts, anion receptors and bimetallic complexes. Chapter 2 discusses new palladium(II) complexes of an acyclic ligand bearing pendant 2-pyridyl-6-methyl arms, N,N_-bis(6-methyl-2-pyridinyl)-2,6-pyridinedicarboxamide (H2LMe). H2LMe formed a dimer [Pd(LMe)]2 when treated with palladium(II) salts and non-ligating bases, but in the presence of DBU the palladium-DBU adduct, Pd(LMe)(DBU), was formed. Reaction of Pd(LMe)(DBU) with methyl iodide resulted in the displacement of the DBU ligand and the concomitant formation of cationic monomeric complex, [PdI(LMe{Me}2)]I and dimeric N-methylpyridinium complex, [Pd(LMe{Me})]2I2. A series of ligands, N,N_-bis(x-tolyl)-2,6-pyridinedicarboxamide (x = 2, 3, 4) (H2Lxtol), bearing ortho-, meta- and para-tolyl groups, was prepared and these were coordinated to palladium(II) in their deprotonated form so that the effect of the pendant pyridine rings and steric environment around the metal on the reactivity of metal derivatives could be investigated. Stable palladium(II) derivatives of the deprotonated H2Lxtol ligands, Pd(Lxtol)(E) (E = DBU, n-butylamine, p-tolylisocyanide) were prepared. The p-tolylisocyanide adducts reacted with pyrrolidine or p-toluidine to afford the stable bis(amino)carbene complexes, Pd(Lxtol)(=C(NH-p-tolyl)(pyrl)) and Pd(Lxtol)(=C(NH-p-tolyl)2), respectively. The coordinated DBU ligands in Pd(Lxtol)(DBU) and Pd(LMe)(DBU) were displaced by n-butylamine to afford the corresponding n-butylamine adducts, and their relative rates of exchange were determined by 1H NMR spectroscopy. Chapter 3 discusses palladium(II) complexes of dicationic N-methylpyridinium ligands prepared by treating H2LMe or the series of ligands, N,N_-bis(x-pyridinyl)-2,6- pyridinedicarboxamide (x = 2, 3, 4) (H2Lxpy) that contain pendant 2-, 3-, or 4-pyridyl groups, with methyl triflate to form [H2LMe{Me}2][OTf]2 or [H2Lxpy{Me}2][OTf]2, respectively. These ligands were coordinated in their deprotonated forms to palladium(II) to give [PdCl(Lxpy{Me}2)]OTf. The chloro ligands in these metallated complexes were displaced on treatment with silver triflate in acetonitrile or water to afford the corresponding solvent adducts. The coordinated solvent molecules in [Pd(LMe{Me}2)(NCCH3)][OTf]2 and [Pd(Lopy{Me}2)(OH2)][OTf]2 could in turn be displaced by p-tolylisocyanide to form isocyanide adducts, [Pd(LMe{Me}2)(CN-ptolyl)][ OTf]2 and [Pd(Lopy{Me}2)(CN-p-tolyl)][OTf]2. Dicationic bis(amino)carbene complexes [Pd(LMe{Me}2)(=C(NH-p-tolyl)2)][OTf]2 and [Pd(Lopy{Me}2)(=C(NH-ptolyl) 2)][OTf]2 were prepared by treating the corresponding isocyanide precursors with p-toluidine. A 1H NMR spectroscopic study was performed to compare the relative rates of reaction of p-toluidine with the neutral tolyl isocyanide complexes Pd(Lxtol)(CN-p-tolyl) and the dicationic isocyanide complexes [Pd(LMe{Me}2)(CN-ptolyl)][ OTf]2 and [Pd(Lopy{Me}2)(CN-p-tolyl)][OTf]2 to determine the influence of the steric and electronic environments on the reactivity of the isocyanide ligand. On deprotonation of the amide groups in [H2LMe{Me}2][OTf]2 and [H2Lopy{Me}2][OTf]2 the neutral free bis(imine) compounds LMe{Me}2 and Lopy{Me}2 could be isolated. Chapter 4 discusses extended acyclic ligands H4LpdnA and H4LSpyA (H4LxA) that were derived from the precursor N,N_-bis(6-acrylamido-2-pyridinyl)pyridine-2,6- dicarboxamide (H4LacrA) through Michael addition of pyrrolidine or 2- mercaptopyridine, respectively, to the acrylyl groups. The double-helical dimers [M(H2LxA)]2 were formed when these ligands were treated with palladium(II) or mercury(II) acetate, and in the presence of DBU the adducts Pd(H2LxA)(DBU) were formed. In the absence of added base, palladium(II) acetate coordinated between the tail amine groups of the ligand H4LpdnA which bears terminal pyrrolidyl groups. Chapter 5 discusses complexes of macrocycles formed from double Michael-type addition of the amines n-butylamine, 2-(aminomethyl)pyridine, 2-(aminoethyl)pyridine, N,N-dimethylethylenediamine and N,N_-bis(2-pyridylmethyl)ethylenediamine to the pendant acrylyl groups of H4LacrA. The macrocycle synthesised from addition of nbutylamine, H4LnBu, reacted with palladium(II) acetate and DBU to form a complex in which palladium was coordinated in the macrocycle headgroup and an aminolactam resulting from hydrolysis of DBU was coordinated on the fourth site of the metal, Pd(H2LnBu)(NH2Lac[7]). A palladium derivative of H4LnBu with a labile water ligand, Pd(H2LnBu)(OH2), was prepared and used for subsequent syntheses of n-butylamine, DBU and p-tolylisocyanide adducts. When treated with p-toluidine, the isocyanide ligand of the macrocyclic p-tolylisocyanide adduct was displaced to form a p-toluidine adduct. Modified macrocycles with other amine donors incorporated into the tail were prepared in order to provide an additional site for metal complexation. The macrocycle with an additional N,N-dimethylamino group, H4Ldmen, reacted with metal salts to form complexes where metallation had taken place at the tail amide groups and the tail amine group interacted with the metal.

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25

Lawrence, Sally. "Early transition metal complexes of pyrazole-derived ligands." Thesis, University of Oxford, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.433560.

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26

Franks, Mark A. "Transition metal complexes containing phenylthiolate and phenolate ligands." Thesis, University of Nottingham, 2011. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.580393.

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Chapter 1 provides an introduction to metalloenzymes that either feature active sites containing Ni-thiolate ligation or utilise phenoxyl radicals to perform their catalytic function, with a particular emphasis on the enzymatic active sites of Ni-containing superoxide dismutase (Ni SOD), [NiFe] hydrogenase and galactose oxidase. Studies concerning low molecular weight complexes of each active site are reviewed and their relevance with respect to enzyme function discussed. Details of the project outline conclude the chapter. Chapter 2 details the syntheses and characterisation of the [Zn(tsalen)] derived complexes [ZneBuLsC3N)], [ZneBuLsC2N)], [ZneBuLsNMe)], [ZneBuLlyl)], [Zn(IBuLsPy2)], [ZneBuLsPhl)], [Zn(IBuLslml)2], [ZneBuLsPy3)2], [Zn(LsC2N)], [Zn(LsNMe)], [Zn(Llyl)], [Zn(LsPy2)] and [Zn(LsPh1)], via Zn(II) templated Schiff- base condensation reactions using two thiosalicylaldehyde derived units and a range of primary amines. The syntheses of 2,4-di-tert-butyl-thiosalicylaldehyde from tert- butyl benzene and three functionalised 1,3-propyldiamines (2-(2-pyridylmethyl)-1,3- propanediamine, 2-(2-pyridylethyl)-I,3-propanediamine and 2-benzyl-I,3- propanediamine) are described. X-ray crystallographic studies demonstrate the successful integration of the additional N-donors into the backbone of the ligand framework at the N-imine position. The range of S2N2, S2N3 and S2N4 ligand sets are shown to adopt an array of coordination geometries about the Zn(II) metal centre providing scope for these ligands in tuning the electronic structures of their Ni- containing complexes. Chapter 3 describes the syntheses and X-ray crystallographic, electrochemical and spectroscopic studies of a series of Ni(II) Schiff-base dithiolate complexes, [Ni(IBuLsC3N)], [Ni(IBuLsc2N)], [NieBuLsNMe)], [NieBuLlyl)], [Ni(IBuLly2)], III [Ni(BuLlhl)], [Ni(BuLs1ml)2], [Ni(tBuLly3h]' [Ni(LsPyl)], [Ni(LsPY2)] and [Ni(LsPhl)] obtained via transmetallation from the analogous [Zn(BuLl)] and [Zn(LsR)] complexes described in Chapter 2. The effect that the additional pendant N-donors have upon the redox properties of the individual complexes are considered with respect to reproducing the structural, spectroscopic and functional properties of NiSOD. Particular attention is focussed on the redox properties of [Ni(BuLsPyl)], [Ni(tBuLsPy2)] and [Ni(BuLsPhl)], which together highlight a rare example of the ability of one N-donor group to assume the role of an endogenous donor upon oxidation. The proposed internal rearrangement of the Ni coordination sphere may encourage the formation of a predominantly metal-based SOMO following the oxidation process. Insight upon how this coordination chemistry relates to the chemistry of the active site of Ni SOD is discussed. Chapter 4 reports the electrochemical and spectroscopic characterisation of a range of binuclear [Ni(LsR)Fe(CO)3] and trinuclear [Ni(LsR){Fe(CO)3h] complexes (R = PhI, PyI and Me) synthesised via the reaction of [Ni(tsalen)]-type complexes, [Ni(LsR)], with Fe2(CO)9. X-ray crystallographic studies show that the complexes incorporate biologically relevant structural elements reminiscent of the active site of [NiFe] hydrogenase, including a binuclear Ni(1l2-S)Fe core featuring a ea. 2.9 A Ni- Fe separation. Chapter 5 details the preparation of a series of Zn(II), Ni(lI) and Cu(lI) Schiff-base diphenolate complexes utilising the two novel pentadentate pro-ligands, [H2tBuLo C3N] and [H2tBuLo NMe]. Cyclic voltammetric, spectroelectrochemical and EPR studies show the Zn(lI) and Cu(lI) complexes support two ligand-based oxidation processes, yielding kinetically inert species possessing phenoxyl radical character. Conversely, the paramagnetic Ni(lI) complexes, [Ni(BuLo NMe)] and IV [Ni(tBuLo C3N)], support both metal and ligand-based oxidation chemistry. The chapter concludes by discussing the relative stability of phenoxyl and phenylthiyl radical ligands by comparison with the redox properties of the analogous Schiff-base Zn(II)-dithiolate complexes described in Chapter 2.

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27

Graham, A. "Binuclear and polynuclear metal complexes with bulky ligands." Thesis, University of Edinburgh, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.651687.

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This thesis presents routes to transition metal complexes of pyridonate and carboxylate ligands. Low nuclearity complexes with triphenyl acetate and 1^strow transition metals of the formula [M₄(OMe)₄(O₂CCPh₃)₄(MeOH)₄] (M = Co, Ni or Zn) have been synthesised and mark a change from reactions with other carboxylates which produce linear trinuclear complexes. Molecular modelling studies investigate the close contacts that arise if triphenyl acetate is incorporated into a linear trinuclear compound to establish whether steric interactions are controlling reactivity. High nuclearity complexes with cobalt and nickel have been, made, many of which extend the range of complexes in which the metal atoms form a centred tricapped trigonal prism. These complexes all contain [M₁₀(OH)₆(O₂CCPh₃)₆(xhp)₆]²⁺ (xhp = a pyridone anion substituted at the six position) core with metal atoms capping the triangular faces of the centred prism. A variant on previous trapped trigonal prisms is also presented, in which the cap metal atoms cap the prism edges. In other complexes the metal atoms form new topologies, ranging from hexa- to octanuclear. In some complexes sodium atoms are also incorporated into the polynuclear cages. Reaction conditions for formation of these cages was investigated. Variation of the metal salt from chloride to nitrate influences both the yield of high nuclearity complexes and the timescale over which they are formed. The choice of recrystallisation solvent affects the cage formed. For example. hexanuclear and heterometallic octanuclear cobalt complexes follow identical syntheses except for the recrystallisation solvent. The means by which counterion and recrystallisation solvent influence reactivity is unclear.

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28

Rivers, Christopher John. "Transition metal complexes incorporating trialkylsilyl substituted pentalene ligands." Thesis, University of Sussex, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.289228.

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29

Harriott, Patrick. "Pendant-arm macrocyclic ligands and their metal complexes." Thesis, Queen's University Belfast, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.336108.

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30

Herring, A. M. "New transition metal complexes containing functionalised phosphine ligands." Thesis, University of Leeds, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.383967.

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31

Rahoo, Haji. "Fluxional characteristics of metal complexes of sulphur ligands." Thesis, University of Exeter, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.280893.

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32

Wood, Andrew John. "Mixed-metal complexes incorporating redox-active cyanomanganese ligands." Thesis, University of Bristol, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.311404.

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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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34

Greatorex, Sam. "Metal complexes of dioxolene and iminonitroxyl radical ligands." Thesis, University of Leeds, 2018. http://etheses.whiterose.ac.uk/21946/.

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This thesis focuses on the design, synthesis and analysis of multinuclear mixed-valent dioxolene complexes and Cu(II) nitroxyl complexes. Chapter 1 contains a review of the relevant literature for the field of mixed-valent dioxolene complexes and molecular magnetism in nitroxyl complexes. Chapter 2 reports the synthesis and crystallographic analysis of a series of novel highly porous solvent-supported supramolecular assemblies of triptycene derivatives. Chapter 3 reports the complexation and characterisation of triptycene derivatives and related multi-dioxolene ligands with Pt(II). Chapter 4 reports the synthesis, complexation and characterisation of a rigid tris(dioxolene) CTC derivative with Pt(II). It also describes the attempted synthesis of coordination polymers containing multi-dioxolene ligands. Chapter 5 reports the synthesis and characterisation of a series of Cu(II) complexes containing the biradical ligand bisimpy. Chapter 6 contains a description of all synthetic procedures undertaken during this work.

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35

Ivison, Peter. "Transition metal complexes of hard-soft donor ligands." Thesis, Kingston University, 1992. http://eprints.kingston.ac.uk/20562/.

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36

Graham, Alasdair. "Dinuclear and polynuclear metal complexes with bulky ligands." Thesis, University of Edinburgh, 2001. http://hdl.handle.net/1842/12051.

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37

Lee, Fu-wa. "Syntheses, structures and reactivity of the group 6 and 7 metal complexes containing chelating nitrogen donor ligands and metal-ligand multiple bonds /." Hong Kong : University of Hong Kong, 1997. http://sunzi.lib.hku.hk/hkuto/record.jsp?B21020255.

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38

Johnson, Donald Martin. "Cyanoscorpionates and Transition Metal Complexes." Digital Commons @ East Tennessee State University, 2010. https://dc.etsu.edu/etd/1725.

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The new dihydrobis(4-cyano-3-tert-butylpyrazolylborate) ligand has been synthesized. Isolated crystals of the thallium complex were collected and structurally characterized by X-ray diffraction. Transition metal complexes of the ligand are currently under investigation.

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39

李富華 and Fu-wa Lee. "Syntheses, structures and reactivity of the group 6 and 7 metal complexes containing chelating nitrogen donor ligands and metal-ligandmultiple bonds." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1997. http://hub.hku.hk/bib/B29872911.

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40

Tripathi, Monika. "Synthesis of ligands and metal complexes incorporating oxyallyl patterns." Thesis, Université Grenoble Alpes (ComUE), 2019. http://www.theses.fr/2019GREAV033.

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Les oxyallyles sont considérés généralement comme des espèces transitoires non observables, mais peuvent être stabilisés par l’introduction de groupements aminés donneurs d’électrons. De tels 1,3-di(amino)oxyallyls sont rédox-actifs et peuvent exister sous jusqu’à trois formes redox. En particulier, leurs cations radicaux sont persistants à l’air, en raison d’un effet capto-datif «extrême». Ce manuscrit décrit nos efforts pour développer des complexes métalliques redox-actifs comportant des motifs oxyallyles, avec une attention particulière pour les ligands de type β-diketiminate (Nacnac). En effet, en général, les complexes de ces derniers se décomposent lors de d’une oxydation/réduction centrée sur le ligand et la conception de version redox-actives représente encore un défi. Le premier chapitre résume la littérature récente concernant les oxyallyles stabilisés et l’étude des ligands redox actifs.Le second chapitre décrit l’oxydation directe de vinamidines par m-CPBA pour former des ligands bis(imino)cétones. Cette approche synthétique représente une amélioration importante par rapport aux méthodologies précédemment décrites. La chimie de coordination et l’électrochimie de ces composés ont également été étudiées.Le troisième chapitre explore l’introduction d’un nouveau motif di(methyl)amino en positions 1 et 3 des bis(imino)cétones. Nous décrivons notamment une étude détaillée de la réaction des sels de 1,3-dichlorovinamidinium avec des dérivés de l’aniline, ainsi qu’une étude préliminaire de la chimie de coordination du nouveau ligand enrichi électroniquement.Le dernier chapitre expose des stratégies et des concepts alternatifs, notamment l’utilisation de ligands O-protégés et/ou bidentés
The stabilization of transient and non-observable oxyallyl intermediates can be achieved through the introduction of electron-donating amino substituents. The resulting 1,3-di(amino)oxyallyls are redox-active and can have up to three persistent redox forms. In particular, their radical cations are even air-persistent, as the result of “enhanced” capto-dative effect. This manuscript reports our efforts for the development of redox-active metal complexes featuring oxyallyl frameworks, with a particular focus on β-diketiminate (NacNac) ligands. Indeed, metal-complexes of the latter generally decompose upon ligand-centered oxidation/reduction and the design of redox-active NacNac remains a challenge. The first chapter summarizes recent bibliography related to stabilized oxyallyl molecules and the study of redox-active ligands.The second chapter describes the direct oxidation of vinamidines with m-CPBA to afford bis-imine ketone ligands. This methodology is far simpler and easier as compared to the previously described method from the literature. The coordination chemistry of these ligands and their redox behavior were also studied.The third chapter explores an original substitution pattern on bis-imine ketones, with the introduction of electron-donating amino groups in 1,3-positions. A detailed study of the reaction of 1,3-dichloro vinamidinium salts with aniline derivatives is reported, as well as preliminary study of the metal coordination of the novel electron-rich ligand.The last chapter presents alternatives strategies and concepts, including the use of O-protected and/or bidentates ligands

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41

Hawkins, I. M. "New transition metal complexes containing phosphine and sulphur ligands." Thesis, University of East Anglia, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.235225.

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42

Phelan, Gregory David. "The synthesis, design, and applications of lanthanide cored complexes /." Thesis, Connect to this title online; UW restricted, 2003. http://hdl.handle.net/1773/8572.

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43

Hagemann, Justin Philip. "Design, synthesis and evaluation of novel, metal complexing agents." Thesis, Rhodes University, 1997. http://hdl.handle.net/10962/d1004965.

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Various chelating ligands have been designed and synthesised; these include amino-amide ligands, tetraacetic acid systems and sulfur-containing amide ligands. Difficulties in the synthesis and purification of the amino-amide ligands were largely overcome, permitting the mono acylation of ethylenediamine and the synthesis of bis(2-aminoethyl)-2-benzylpropanediamide. Novel tetraacetic acid ligands, based on the propanediamide backbone and targeted as EDTA analogues, were obtained from their methyl and benzyl esters; but the instability of the tetraacids prevented their full characterisation. Bidentate, tridentate and tetradentate sulfur-containing monoamide ligands, based on the ortho-thio acetanilide moiety, were designed to specifically chelate platinum and palladium in the presence of base metals. In their synthesis, thiocyanation was used to introduce the orth-thio group on para-substituted anilines, and further functionalisation was achieved via appropriate protection of nucleophilic sulfur moieties. A range of tetradentate, sulfur-containing diamide ligands was also synthesised by reacting substituted 2-mercaptoacetanilides with 1,2- dibromoethane. Novel ligands were characterised by spectroscopic (¹H and ¹³C NMR; IR and M S) techniques and elemental (combustion and high resolution MS) analysis. Computer modelling and ¹H NMR chemical shift data have been used to explore the conformational preferences of the sulfur-containing acetanilide ligands. The macrocyclic ligands and systems with ortho-methylthio substituents appear to exhibit the greatest degree of coplanarity of the aromatic and amide functions. Solvent extraction studies revealed that the sulfur-containing amide ligands selectively extracted palladium(II) from platinum(II), copper(II}, nickel(II} and cobalt(II}. Even though the palladium(II} was extracted from an acidic medium, certain monoamide ligands were able to complex palladium(II) through their sulfur and deprotonated amide nitrogen donors, a trithia monoamide ligand being observed to displace all the chloride ligands on palladium to form a monomeric tetracoordinate complex. The diamide ligands, however, appeared to favour extraction of palladium(II) by coordination through their sulfur donors, forming 5-membered sulfur-sulfur chelates. In basic media (pH 8-9), selected sulfur-containing monoamide and diamide ligands have been shown to complex platinum(II) and palladium(II) through their sulfur and deprotonated amide nitrogen donors. At neutral pH, a dimercapto monoamide ligand has been shown to complex platinum from cisplatin with partial expulsion of the ammine ligands, while a macrocyclic trithia monoamide ligand has been observed to complex platinum from tetrachloroplatinate with concomitant deprotonation of the amide nitrogen. Where possible, the complexes were characterised by infrared and ¹H NMR spectroscopy and have also been studied using the computer modelling soft-ware programmes, Momec® and Hyperchem®.

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Hao, Haijun. "Non-Cp Metal complexes Supported by Nitrogen Donor Ligands." Doctoral thesis, [S.l.] : [s.n.], 2001. http://hdl.handle.net/11858/00-1735-0000-0006-AE9A-C.

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45

Cade, Ian Alexander. "Antenna modified ethynyl benzene ligands and their metal complexes." Thesis, Imperial College London, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.417275.

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46

Ahmed, Aminu. "Mixed donor carbene pyridyl ligands and their metal complexes." Thesis, Cardiff University, 2008. http://orca.cf.ac.uk/54889/.

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This thesis describes the synthesis of a series of Ag(I), Pd(II), Rh(I) and Ir(I) complexes of quinoline functionalised nucleophilic heterocyclic carbene (NHC) ligands. The transmetallation properties of the Ag(I) complexes were utilised to prepare the corresponding Pd(II), Rh (I) and Ir(I) (NHC) complexes. A series of quinoline based imidazolium, pyrimidinium salts were prepared and characterised as NHC ligand precursors. Ag(I)(NHC) complexes were prepared by the reaction of the quinoline functionalised salts with Ag20 in DCM. All complexes were spectroscopically characterised and the results of single X- ray crystallographic studies are reported for two of the complexes and the geometry around the silver cation was observed to be distorted linear. Two quinoline based palladium (II) (NHC) complexes were prepared via transmetallation Ag(I)(NHC) complexes is reported. The synthesis of a series of methylene bridged quinoline functionalised Rh (I) and Ir(I) (NHC) complexes through transmetallation of the Ag(I)(NHC) complexes is reported and the results of single X-ray crystallographic studies are reported for most of the complexes showing consistent pattern in term of bond lengths and angles. Two of the Ir(I) (NHC) complexes were tested as catalysts in transfer hydrogenation reactions, showing good activity at low Ir loadings.

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47

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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48

Harkup, Kathryn. "Studies in tridentate hemilabile ligands and their metal complexes." Thesis, University of Nottingham, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.406977.

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49

Chung, Simon S. M. "Transition metal complexes of new mixed donor tridentate ligands." Thesis, University of Nottingham, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.367415.

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50

Forder, Robin James. "Transition metal complexes of phosphine and mixed phosphathia ligands." Thesis, University of Southampton, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.243129.

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Dissertations / Theses on the topic 'Metal complexes Metal complexes Ligands'

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