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The preparation and use of metal salen complexes derived from cyclobutane diaminePatil, Smita S. January 1900 (has links)
Doctor of Philosophy / Department of Chemistry / Christopher J. Levy / The helix is an important chiral motif in nature, there is increasing development in field of helical transition metal complexes and related supramolecular structures. Hence, the goals of this work are to apply the principles of helicity in order to produce metal complexes with predictable molecular shapes and to study their properties as asymmetric catalysts.
Computational studies suggest that the (1R,2R)-cyclobutyldiamine unit can produce highly twisted salen complexes with a large energy barrier between the M and P helical forms. To test this prediction, the tartrate salt of (1R,2R)-cyclobutyldiamine was synthesized and condensed with a series of saliclaldehydes to produce novel salen ligands. The salicylaldehydes chosen have extended phenanthryl or benz[a]anthryl sidearms to encourage formation of helical coordination complexes. These ligands were metallated with zinc, iron and manganese salts to produce salen metal complexes which were characterized by NMR analysis, high-resolution mass spectrometry, and IR spectroscopy.
A second ligand type, neutral bis(pyridine-imine) has also been synthesized from (1R,2R)-cyclobutyldiamine and quinolylaldehydes. The synthesis of bis(pyridine-imine) ligands was conducted using greener method, solvent assisted grinding. These ligands, in-situ with nickel metal salts, showed good catalytic activity for asymmetric Diels-Alder reactions.
The third ligand type studied was chiral acid-functionalized Schiff-base ligands. These were synthesized by the condensation of 3-formyl-5-methyl salicylic acid and (1R,2R)-cyclobutyldiamine. With this type of ligand, there is possibility of producing both mono and dinuclear metal complexes. In our studies, we were only able to synthesize mononuclear complexs. These were tested as catalysts for asymmetric direct Mannich-type reaction, but were found to be ineffective.
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Structure and reactivity of transition metal clustersHermes, A. C. January 2013 (has links)
A range of computational and experimental techniques have been applied to the study of four metal cluster systems. Decorated rhodium clusters Rh n O m (N 2 O) + ( n = 4 − 8, m = 0 − 2) have been investigated both experimentally by IR-MPD and computationally using DFT. The effect of cluster size as well as oxygen coverage on the spectroscopy of the N 2 O bend are analyzed. The infrared-induced decomposition of N 2 O on Rh n O + m is observed on all cluster sizes, with marked differences as a function of size and oxygen coverage, particularly in the case of Rh 5 (N 2 O) + . The oxidation of CO was studied on the surface of small platinum cluster cations Pt n O + m ( n = 3 − 7, m = 2 , 4) by IR-MPD at 400 – 2100cm −1 . Spectroscopically, oxygen is found to be bound both dissociatively and molecularly on the cluster surface, while the CO band is found to red shift in cluster size, and blue shift with oxygen coverage. Oxidation of CO proceeds on all cluster sizes, with a constant branching ratio of 40% : 60% . DFT calculations identified key stationary points and barriers on the Pt 4 O 2 CO + reaction pathway. The one-colour Ta 2 photodissociation is studied by photoionization and VMI in the range 23500 – 24000cm −1 , finding clear evidence of a fragmentation process producing Ta , which is interpreted as fragmentation of cationic Ta + 2 at the two photon level. A majority of the observed channels produce either atomic ( Ta( 4 F 3/2 ) ) or cationic ( Ta + ( 5 F 1 ) ) ground state. An improved value for the dissociation energy D 0 ( Ta + 2 ) is obtained, in agreement with computational predictions. The anisotropies observed show weak evidence of a perpendicular transition being involved in the photodissociation process. Finally, the photodissociation dynamics of Cu 2 are studied by spectroscopy in the range 36000 – 38200cm −1 as well as VMI. Clear evidence for resonant photolysis of Cu 2 is obtained, as a result of both direct dissociation of the Cu + 2 2 Π ion state as well as dissociation of doubly excited Cu 2 states, which leads to a determination of dimer dissociation energies. Finally, the production of Cu + 2 is interpreted as evidence of photolysis of Cu 3 , from which a Cu 3 dissociation energy is derived.
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Electromechanical properties of atomically thin materialsPearce, Alexander James January 2014 (has links)
We discuss the effect of elastic deformations on the electronic properties of atomically thin materials, with a focus on bilayer graphene and MoS2 membranes. In these materials distortions of the lattice translate into fictitious gauge fields in the electronic Dirac Hamiltonian that are explicitly derived here for arbitrary elastic deformations, including in-plane as well as flexural (out-of-plane) distortions. We consider bilayer graphene, where a constant fictitious gauge field causes a dramatic reconstruction of the low energy trigonally warped electronic spectrum inducing topological transitions in the Fermi surface. We then present results of ballistic transport in trigonally warped bilayer graphene with and without strain, with particular focus on noise and the Fano factor. With the inclusion of trigonal warping the Fano factor at the Dirac point is still F = 1/3, but the range of energies which show pseudo diffusive transport increases by orders of magnitude compared to the results stemming out of a parabolic spectrum and the applied strain acts to increase this energy range further. We also consider arbitrary deformations of another two-dimensional membrane, MoS2. Distortions of this lattice also lead to a fictitious gauge field arising within the Dirac Hamiltonian, but with a distinct structure than seen in graphene. We present the full form of the fictitious gauge fields that arise in MoS2. Using the fictitious gauge fields we study the coupling between electronic and mechanical degrees of freedom, in particular the coupling between electrons and excited vibrational modes, or vibrons. To understand whether these effects may have a strong influence on electronic transport in MoS2 we calculate the dimensionless electron-vibron coupling constant for all vibron modes relevant for electronic transport. We find that electron-vibron coupling constant is highly sample specific and that the longitudinal stretching mode is the vibron with the dominant coupling. This however reaches maximum values which are lower than those observed in carbon nanostructures.
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Synthesis of IV-VI Transition Metal Carbide and Nitride Nanoparticles Using a Reactive Mesoporous Template for Electrochemical Hydrogen Evolution ReactionAlhajri, Nawal Saad 01 1900 (has links)
Interstitial carbides and nitrides of early transition metals in Groups IV-VI exhibit platinum-like behavior which makes them a promising candidate to replace noble metals in a wide variety of reactions. Most synthetic methods used to prepare these materials lead to bulk or micron size powder which limits their use in reactions in particular in catalytic applications. Attempts toward the production of transition metal carbide and nitride nanoparticles in a sustainable, simple and cheap manner have been rapidly increasing. In this thesis, a new approach was presented to prepare nano-scale transition metal carbides and nitrides of group IV-VI with a size as small as 3 nm through the reaction of transition metal precursor with mesoporous graphitic carbon nitride (mpg-C3N4) that not only provides confined spaces for nanoparticles formation but also acts as a chemical source of nitrogen and carbon.
The produced nanoparticles were characterized by powder X-ray diffraction (XRD), temperature-programmed reaction with mass spectroscopy (MS), CHN elemental analyses, thermogravimetric analyses (TGA), nitrogen sorption, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM).
The effects of the reaction temperature, the ratio of the transition metal precursor to the reactive template (mpg-C3N4), and the selection of the carrier gas (Ar, N2, and NH3) on the resultant crystal phases and structures were investigated.
The results indicated that different tantalum phases with cubic structure, TaN, Ta2CN, and TaC, can be formed under a flow of nitrogen by changing the reaction temperatures. Two forms of tantalum nitride, namely TaN and Ta3N5, were selectively formed under N2 and NH3 flow, respectively. Significantly, the formation of TaC, Ta2CN, and TaN can be controlled by altering the weight ratio of the C3N4 template relative to the Ta precursor at 1573 K under a flow of nitrogen where high C3N4/Ta precursor ratio generally resulted in high carbide content rather than nitride.
In addition, the reactivity of the transition metals of group IV-VI with the reactive template was investigated under a flow of N2 at different temperatures in the range of 1023 to 1573 K while keeping the weight ratio constant at 1:1. The results show that Ti, V, Nb, Ta, and Cr reacted with mpg-C3N4 at 1023 K to form nitride phase with face centered cubic structure. The nitride phase destabilized at higher temperature ≥1223 K through the reaction with the remaining carbon residue originated from the decomposition of the template to form carbonitride and carbide phases. Whereas, Mo and W produce a hexagonal structure of carbide irrespective of the applying reaction temperature. The tendency to form transition metal nitrides and carbides at 1023 K was strongly driven by the free energy of formation. The observed trend indicates that the free energy of formation of nitride is relatively lower for group IV and V transition metals, whereas the carbide phase is thermodynamically more favorable for group VI, in particular for Mo and W. The thermal stability of nitride decreases at high temperature due to the evolution of nitrogen gas. The electrocatalytic activities of the produced nanoparticles were tested for hydrogen evolution reaction in acid media and the results demonstrated that molybdenum carbide nanoparticles exhibited the highest HER current with over potential of 100 mV vs. RHE, among the samples prepared in this study. This result is attributed to the sufficiently small particle size (8 nm on average) and accordingly high surface area (308 m2 g-1). Also, the graphitized carbon layer with a thickness of 1 nm on its surface formed by this synthesis provides excellent electron pathway to the catalyst which will improve the rate of electron transfer reaction.
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New transition metal carbene complexes for application in homogeneous catalysisJulius, Gerrit R. 12 1900 (has links)
Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch,2005. / This study comprises the preparation and full characterisation of new carbene complexes of group
10 metals (Ni, Pd or Pt), the group 9 metal, rhodium, as well as group 6 metals (Cr and/or W).
N-heterocyclic carbene (NHC) complexes of nickel and palladium were prepared via oxidative
addition of the corresponding carbene precursors imidazolium-, imidazolinium-, pyridinium- and
quinolinium chloride salts, to M(PPh3)4 (M = Ni or Pd). Three types of carbene complexes, namely
the standard five-membered two-N carbene complexes, new six-membered NHC complexes and
novel six-membered rNHC complexes received attention. In the rNHC complexes the heteroatom
(N) is removed from the carbene carbon. These new square planar carbene complexes of the general
formula trans-[(PPh3)2MCl(L)]X (M = Ni or Pd; X = BF4 or PF6) L = 1,3-dimethyl-2,3-dihydro-1Himidazol-
2-ylidene, 1,3-dimethyl-2,3,4,5-tetrahydro-1H-imidazol-2-ylidene, 1-methyl-1,2-dihydropyridin-
2-ylidene, 1-methyl-1,2-dihydro-quinolin-2-ylidene, 1,4-dimethyl-1,2-dihydro-quinolin-2-
ylidene, 2-methoxy-1-methyl-1,4-dihydro-quinolin-4-ylidene, 1-methyl-1,4-dihydro-pyridin-4-
ylidene) have been isolated and characterised. The preparation of the corresponding carbene
complexes of platinum was complicated by the formation of [PtCl(PPh3)3]BF4 and the desired
carbene complexes could not be isolated in pure form. The investigation of rNHC complexes was
extended to include the synthesis of (CO)5M{CSC(CNCMe2CH2O)CHCH} (M = Cr and W).
The molecular and crystal structures of thirteen of the new carbene complexes including the
structures of both cis- (only formed below –20°C) and trans-chloro(1-methyl-1,2-dihydro-quinolin-
2-ylidene)bis(triphenylphosphine)palladium(II) tetrafluoroborate were determined. The metalcarbene
bond distances in both the palladium and nickel carbene families do not differ significantly.
The carbene ligands can be arranged in a series of increasing trans-influence, using the metalchloride
bond distance as a guideline, as follows: 1,3-dimethyl-2,3-dihydro-1H-imidazol-2-ylidene
and 1,3-dimethyl-2,3,4,5-tetrahydro-1H-imidazol-2-ylidene < 1-methyl-1,2-dihydro-pyridin-2-
ylidene < 2-methoxy-1-methyl-1,4-dihydro-quinolin-4-ylidene, 1-methyl-1,4-dihydro-pyridin-4-
ylidene. The crystal and molecular structures of two platinum compounds, cis-chloro(2-methoxy-1-
methyl-1,4-dihydro-quinolin-4-ylidene)bis(triphenylphosphine)platinum(II) tetrafluoroborate and
the byproduct [PtCl(PPh3)3]BF4 were also determined. Trans-chloro(2-methoxy-1-methyl-1,4-dihydro-quinolin-4-ylidene)bis(triphenylphosphine)
palladium(II) tetrafluoroborate was found to be a very active catalyst, compared to simpler
palladium carbene and phosphine complexes, in the Mizoroki-Heck and Suzuki-Miyaura coupling
reactions. Quantum mechanical calculations indicated that the rNHC ligand in this complex is
bound stronger to the palladium than a standard imidazole-derived NHC ligand. Further
calculations suggested that the remote heteroatom carbene (rNHC) complexes of nickel(II) are
significantly more stable when compared to the normal carbene (NHC) complexes. Energy
decomposition analysis suggested that the rNHC ligands are strong s-donors and weak -acceptors.
Unsymmetrical imidazolium-derived bis(carbene) complexes, [Rh(NHC)2COD]Br, bromomono(
carbene) complexes, Rh(Br)COD(NHC), and chloro-mono(carbene) complexes,
Rh(Cl)COD(NHC) where NHC = 1-R-3-methyl-2,3-dihydro-1H-imidazol-2-ylidene (R = ethyl,
propyl or butyl), were formed in each reaction of the corresponding free carbene ligand with
[Rh(Cl)COD]2. [Rh(Br)COD(NHC)] formed as a result of substitution of a chloride ligand by a Br--
anion. The carbonyl complexes, cis-[Rh(CO)2X(NHC)] (X = Br or Cl; NHC = 1-ethyl-3-methyl-
2,3-dihydro-1H-imidazol-2-ylidene) were isolated after the substitution of the COD ligand in
Rh(X)COD(NHC) (X = Br or Cl) with CO. Isomerisation of these cis-carbonyl complexes to the
trans isomers was observed.
Cis-[(h4-1,5-cyclooctadiene)bis(1-butyl-3-methyl-2,3-dihydro-1H-imidazol-2-ylidene)rhodium(I)]
bromide, bromo(h4-1,5-cyclooctadiene)(1-methyl-3-propyl-2,3-dihydro-1H-imidazol-2-ylidene)
rhodium(I) and cis-[(h4-1,5-cyclooctadiene)bis(1-butyl-3-methyl-2,3-dihydro-1H-imidazol-2-
ylidene)rhodium(I)]bromide were also characterised by single crystal X-ray diffraction.
The synthesis and structural characterisation of a series of acyclic and heterometallacyclic Fischertype
carbene complexes in which a soft donor atom (P) attached to the carbene side chain is either
uncoordinated, (CO)5M=C(NMe2)CH2PPh2 (M = Cr or W), bonded to the original central metals (Cr
or W) in four-membered chelates, (CO)4M=C(NMe2)CH2PPh2, or coordinated to a second M(CO)5
unit (only isolated for chromium) (CO)5Cr=C(NMe2)CH2P(Ph2)Cr(CO)5, were carried out. These
compounds were produced by the reaction of the anionic Fischer-type aminocarbene complexes,
[(CO)5Cr=C(NMe2)CH2]Li (M = Cr or W), with ClPPh2. The formation of the four-membered
chelates, via cyclisation, occurs much faster for Cr than for W. The aminocarbene-phosphine chelates represent the first examples of structurally characterised, four-membered C,P-chelate
carbene complexes.
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The chemistry of ruthenium carbonyl clusters containing nitrene and nitrido ligands何毅雯, Ho, Ngai-man, Emmie. January 2000 (has links)
published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy
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Synthesis and luminescence studies of branched carbonrich platinum(II)and palladium(II) alkynyl complexes: versatile building blocks for multinuclear assembliesTao, Chi-hang., 陶志恆. January 2004 (has links)
published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy
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Transition metal catalyzed cyclization and synthesis of triptolide analogsPan, Jiehui., 潘杰輝. January 2006 (has links)
published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy
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Density functional theory studies of selected transition metals catalyzed C-C and C-N bond formation reactionsLin, Xufeng., 林旭鋒. January 2007 (has links)
published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy
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Design, synthesis, and photophysical and electrochemical studies of redox-active macrocyclic dinuclear transition metal complexes aspotential molecular switchesKong, Jianfei., 孔建飞. January 2009 (has links)
published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy
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