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Student Number : 9006831D - PhD thesis - School of Chemistry - Faculty of Science / The ligand substitution reactions of aquacobalamin are fast and hence the usual inertness of the d6 Co(III) ion has been modified. It is well established that the reactions proceed through a dissociative interchange mechanism; however, previous ligand studies were performed in a KCl medium, which led to the formation of the more substitution-inert chloro complex. The kinetics of aquacobalamin were reinvestigated with the ligands N3–, NO2–, SCN–, S2O32–, OCN– and SeCN– in a NaNO3 medium. The reactions proceeded too rapidly for saturation kinetics to be observed and hence only the second-order rate constants could be obtained. These were corrected for pH and determined as a function of temperature, from which the activation parameters were determined. The donor atom of the ambidentate ligands were investigated and correlations were found between the Mulliken population on the donor atom, the energy of the highest occupied molecular orbital (HOMO) with σ symmetry, and Δ, the enthalpy of activation, and Δ, the entropy of activation, respectively. Good correlations occurred when the donor atoms were taken to be N for SCNII‡kHII‡kS– and NO2–; S for S2O32–; O for OCN– and Se for SeCN–. The effect that changing the environment of aquacobalamin has on its kinetics was observed by determining the rate constants for the reaction of pyridine with aquacobalamin in water and 70% ethanol. The rates were faster in water and the activation parameters obtained for the reaction of aquacobalamin with pyridine in 70% ethanol are larger than they are for the reaction in water. The larger ΔH‡ arises due to less bond formation between pyridine and Co in the transition state and ΔS‡ is larger because it is dominated by the freeing of the coordinated water i.e. bond breaking is the dominant process in the transition state. The effects of a bulkier ligand than water on the kinetics of aquacobalamin were investigated. The temperature dependence of the kinetics of the substitution of I– in iodocobalamin by imidazole, N3– and S2O32– was studied. Despite the increase in size of the departing ligand there is still nucleophilic participation of the incoming ligand in the transition state and hence the reaction still proceeds via an Id mechanism. In order to probe the cis-effect of the corrin in vitamin B12 derivatives, comparative studies were undertaken of the reactions of aquacobalamin and aqua-10-Xcobalamin, X = Cl, NO, NH2, where the H at C10 was replaced with an electron-donating (Cl, NH2) or electron-withdrawing (NO) group. Formation constants were obtained for aquacobalamin and aqua-10-chlorocobalamin for the substitution of coordinated H2O with various anions (N3–, NO2–, SCN–, S2O32–, OCN–, SeCN–) and neutral N-donor ligands (CH3NH3, pyridine, imidazole). The anionic ligands bind more strongly to aqua-10-chlorocobalamin than to aquacobalamin with log K values larger by between 0.10 and 0.63 (average 0.26) larger. The converse is true for the neutral N-donor ligands, where log K is smaller by between 0.17 and 0.3 (average 0.25). Semi-empirical molecular orbital (SEMO) calculations using the ZINDO/1 model on the hydroxo complexes show that charge density is delocalised from the axial donor atom to the metal and Cl. Thus the anionic ligands bind more strongly to aqua-10-chlorocobalamin because of the ability of the metal and the Cl at C10 to accept charge density from the ligand. The cobalt ion in aqua-10-chlorocobalamin is more electron rich than it is in aquacobalamin and so it is less likely to accept further electron density from a neutral axial donor ligand. This results in the stability being lower than that of aquacobalamin. The reaction kinetics of the substitution of H2O in aqua-10-chlorocobalamin were determined for the ligands N3– and pyridine. The reaction proceeds via a dissociative interchange mechanism since saturation was seen for pyridine and not for N3–. The activation parameters, ΔH‡ and ΔS‡, are lower for aqua-10-chlorocobalamin than aquacobalamin and hence it can be deduced that bond breaking between the coordinated water and the cobalt atom is more dominant in aquacobalamin. The rates of reaction are faster for aquacobalamin than they are for aqua-10-chlorocobalamin. SEMO calculations show that as the Co–O bond is stretched, the charge density on Co in aquacobalamin is always lower than that on aqua-10-chlorocobalamin, suggesting that aquacobalamin is a better electrophile towards the incoming ligand, thereby explaining the faster kinetics. Aqua-10-nitrosocobalamin was synthesised and characterised by FAB(MS), NMR and UV-vis spectroscopy. The strongly electron-withdrawing NO group has deactivated the metal ion towards ligand substitution, with neither 1.2 M pyridine nor 0.7 M N3– showing any spectroscopic evidence for the displacement of the axial H2O ligand. This provides further evidence that the electronic structure of the corrin ring can directly influence the ligand-binding properties of the metal. Aqua-10-aminocobalamin was synthesised from aqua-10-nitrosocobalamin but is unstable in solution. Hence, only a preliminary UV-vis study could be undertaken with the compound. This study shows that the shifts in the bands occur towards longer wavelengths than that of aqua-10-chlorocobalamin, suggesting that the amino group at the C10 position donates more electron density to the cobalt centre than the chloro group.

Pulsed laser time-resolved ligand-substitution photochemistry for (DTO)W(CO)4, (DTN)W(CO)4, and (NP)Mo(CO)4 (DTO = 2,2,7,7-tetramethyl-3,6-diathiaoctane; DTN = 2,2,8,8- tetramethyl-3,7-diathianonane; NP = l-diethylamino-2- diphenylphosphinoethane) proceeds via initial fission of the W-S and Mo-P bonds, affording Cs and C4v five-coordinate intermediates for DTN and NP but largely Cs for DTO. The rates of reaction of these intermediates, via chelate ring closure and competitive bimolecular interaction with Lewis bases (= L, alkylphosphines and alkyl phosphites) for the Cs intermediates and via bimolecular interaction of L with the C4v intermediates, together with activation parameters for these processes have been determined. The rates of interactions at the Cs intermediates are significantly faster than at the C4v intermediates.

Thesis advisor: Chia-Kuang (Frank) Tsung / Exchange reactions have enabled a new level of control in the rational, stepwise preparation of metal-organic framework (MOF) materials. However, their full potential is limited by a lack of understanding of the molecular mechanisms by which they occur. This dissertation describes our efforts to understand this important class of reactions in two parts. The first reports our use of a linker exchange process to encapsulate guest molecules larger than the limiting pore aperture of the MOF. The concept is demonstrated, along with evidence for guest encapsulation and its relation to a dissociative linker exchange process. The second part describes our development of the first quantitative kinetic method for studying MOF linker exchange reactions and our application of this method to understand the solvent dependence of the reaction of ZIF-8 with imidazole. This project involved the collection of the largest set of rate data available on any MOF linker exchange reaction. The combination of this dataset with small molecule encapsulation experiments allowed us to formulate a mechanistic model that could account for all the observed kinetic and structural data. By comparison with the kinetic behavior of complexes in solution, we were able to fit the kinetic behavior of ZIF-8 into the broader family of coordination compounds. Aside from the specific use that our kinetic data may have in predicting the reactivity of ZIF linker exchange, we hope that the conceptual bridges made between MOFs and related metal−organic compounds can help reveal underlying patterns in behavior and advance the field. / Thesis (PhD) — Boston College, 2017. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

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ABSTRACT AXIAL LIGAND SUBSTITUTION REACTION KINETICS OF PYRIMIDINE-2-THIONATO BRIDGED BINUCLEAR PLATINUM(III) COMPLEXES G&ouml / y, Aytun&ccedil / M. S. Department of Chemistry Supervisor: Prof. Dr. H&uuml / seyin iS&ccedil / i Co-supervisor: Assoc. Prof.Dr. Seniz &Ouml / zalp Yaman September 2007, 89 pages The kinetics of the ligand substitution reactions, which is represented by the equation, [Pt2(C4H3N2S)4X2] + 2Y- Pt2(C4H3N2S)4Y2 + 2X- where X- = Cl-, Br-, I- and Y- = Cl-, Br-, I- are studied in acetonitrile in the presence of excess Y- ion concentrations, under constant ionic strength. All reactions are reversible. The rate of the above reaction is dependent on binuclear complex and entering ligand concentrations. Thus general rate equation can be written as Rate = k [Y-]a[Pt2(C4H3N2S)4X2]b The reaction rates are first order with respect to the substrate complex (b=1). The experimentally determined values of the order of the reaction with repect to entering ligand, &ldquo / a&rdquo / , are 0.96&plusmn / 0.057 (X=I-, Y=Cl-), -0.49&plusmn / 0.037 (X=Cl-, Y=I-), 0.28&plusmn / 0.023 (X=I-, Y=Br-), 0.48&plusmn / 0.044 (X=Br-, Y=I-), 0.53&plusmn / 0.042 (X=Br-, Y=Cl-), and -0.21&plusmn / 0.014 (X=Cl-, Y=Br-). The rate constants are 12.1&plusmn / 2.05 M-1s-1 (X=I-, Y=Cl-), (5.7&plusmn / 1.6)x10-3 M1/2s-1 (X=Cl-, Y=I-), 0.3&plusmn / 0.27 M-0.3s-1 (X=I-, Y=Br-), 0.53&plusmn / 0.11 M-1/2s-1 (X=Br-, Y=I-), 1.74&plusmn / 0.16 M-1/2s-1 (X=Br-, Y=Cl-), and 1.71&plusmn / 0.37x10-2 M0.2s-1 (X=Cl-, Y=Br-). To obtain information about the energetics of the reactions, the temperature dependence of the rate constants is determined and the activation parameters &amp / #916 / H* and &amp / #916 / S* are calculated. The values &amp / #916 / S* are negative and, in the range of -81 and -236 J K-1 mol-1. These results support an associative-interchange, Ia, mechanism. All data obtained in this work are used to propose a mechanism which will be consistent with the experimentally determined rate law.

N,N&rsquo / -bis(ferrocenylmethylene)ethylenediamine was prepared from the reaction of ferrocenecarboxaldehyde and ethylenediamine and characterized by IR, Raman, 1H and 13C-NMR spectroscopy. The electrochemical behaviour of this ligand was also studied for the first time by cyclic voltammetry. Diferrocenyl diimine ligand was used in the thermal substitution of 1,5-cyclooctadiene in Cr(CO)4(2:2-1,5-cyclooctadiene) at 38&deg / C in toluene for two hours to form the tetracarbonyl[N,N&rsquo / -bis(ferrocenylmethylene)ethylenediamine]chromium(0), [Cr(CO)4(BFEDA)]. This complex was succesfully isolated and crystallized from its 1:1 toluene/dichloromethane solution and characterized by elemental analysis, MS, IR, 1H, 13C-NMR spectroscopy. Electrochemical behaviour of the complex was also studied by cyclic voltammetry and the mechanism of electrode reaction was investigated by in-situ UV-VIS and IR spectroscopy measurements. This new complex has the iron atom of ferrocene unit in conjugation with the chromium metal center and, therefore, shows an electronic communication between two metal atoms.

The kinetics of ligand substitution for CO in Co4(CO)10(mu4-PPh2) , 1, have been investigated for the ligands P(OMe)3, P(OEt)3, PPh2H, P(0-i-Pr)3, P(n-Bu)3, PPh3, P(i-Pr)3, and PCy3 over a wide temperature range.

The correlation between NMR chemical shifts of interstitial atoms and electronic structures of boron- and carbon-centered hexazirconium halide clusters was investigated by density functional theory (DFT) calculation. The influences of bridging halide and terminal ligand variations on electronic structure were examined respectively. Inverse proportionality was found between the chemical shifts and the calculated energy gaps between two Kohn-Sham orbitals of t1u symmetry, which arose from the bonding and antibonding interaction between the zirconium cage bonding orbitals and the interstitial 2p orbitals. Chemical shielding properties of the interstitial atoms were calculated with Gauge Including Atomic Orbital (GIAO) method. Stepwise ligand substitution of terminal chlorides on [(Zr6CCl12)Cl6]4-cluster by tri(n-butyl)-phosphine oxide (Bu3PO) was conducted with the aid of TlPF6. Composition of the reaction mixtures was analyzed by use of both 13C and 31P NMR. A preliminary scheme for synthesis and separation of [(Zr6CCl12)Cl6-x(Bu3PO)x]x-4 (x = 3 ?? 5) mixture based on solubility difference was reevaluated. Three 1,10-phenanthroline based bidentate ligands, namely, 2,9-Bis(diphenyl-phosphinyl)-1,10-phenanthroline, 2,9-Bis(diethoxyphosphoryl)-1,10-phenanthroline, and 2,9-Bis(di-n-butoxyphosphoryl)-1,10-phenantholine, were synthesized for bridge-chelating the hexazirconium clusters. Coordination chemistry of these ligands with the [Zr6BCl12] and [Zr6CCl12] clusters was subject to preliminary investigation.

The correlation between NMR chemical shifts of interstitial atoms and electronic structures of boron- and carbon-centered hexazirconium halide clusters was investigated by density functional theory (DFT) calculation. The influences of bridging halide and terminal ligand variations on electronic structure were examined respectively. Inverse proportionality was found between the chemical shifts and the calculated energy gaps between two Kohn-Sham orbitals of t1u symmetry, which arose from the bonding and antibonding interaction between the zirconium cage bonding orbitals and the interstitial 2p orbitals. Chemical shielding properties of the interstitial atoms were calculated with Gauge Including Atomic Orbital (GIAO) method. Stepwise ligand substitution of terminal chlorides on [(Zr6CCl12)Cl6]4-cluster by tri(n-butyl)-phosphine oxide (Bu3PO) was conducted with the aid of TlPF6. Composition of the reaction mixtures was analyzed by use of both 13C and 31P NMR. A preliminary scheme for synthesis and separation of [(Zr6CCl12)Cl6-x(Bu3PO)x]x-4 (x = 3 ?? 5) mixture based on solubility difference was reevaluated. Three 1,10-phenanthroline based bidentate ligands, namely, 2,9-Bis(diphenyl-phosphinyl)-1,10-phenanthroline, 2,9-Bis(diethoxyphosphoryl)-1,10-phenanthroline, and 2,9-Bis(di-n-butoxyphosphoryl)-1,10-phenantholine, were synthesized for bridge-chelating the hexazirconium clusters. Coordination chemistry of these ligands with the [Zr6BCl12] and [Zr6CCl12] clusters was subject to preliminary investigation.