Author : Joseph Yoon
Publisher :
ISBN 13 :
Total Pages : 91 pages
Book Rating : 4.:/5 (126 download)
Book Synopsis Longer-lived Olefin Metathesis Catalysts Based on Molybdenum and Ruthenium by : Joseph Yoon
Download or read book Longer-lived Olefin Metathesis Catalysts Based on Molybdenum and Ruthenium written by Joseph Yoon and published by . This book was released on 2020 with total page 91 pages. Available in PDF, EPUB and Kindle. Book excerpt: The field of olefin metathesis has seen considerable growth in the recent past. Some of the earliest milestones in the field include the synthesis of well-defined catalysts based on molybdenum, tungsten, and ruthenium. The efficiencies of these catalysts, however, are limited by their decomposition. Efforts have been made to increase the lifetime of these catalysts by changing the ligand sphere, to stabilize catalytic intermediates. Examples include the employment of the N-heterocyclic carbene (NHC) and the chelating (o-isopropoxy)benzylidene ligand seen in the second-generation Grubbs and Hoveyda catalysts. Processes that utilize the olefin metathesis processes, like those in the petroleum industry and large-scale production of chemicals, are bound by the need for high catalyst loadings which translate to high costs. The work herein presents the pursuit of longer-lived olefin metathesis catalysts based on molybdenum and ruthenium. The first goal of this thesis project was to develop a stable molybdenum-based olefin metathesis catalyst supported by a tridentate PONOP ligand and a chelating (o- x methoxy)benzylidene ligand. Previous attempts in our lab employed nonchelating alkylidene initiators - yielding no success in isolation. The rationale behind this design was that a chelating ether moiety will stabilize the molybdenum-center enough to be isolable. Attempts to isolate the chelating molybdenum-alkylidene species were also unsuccessful. Instead, we probed the in-situ ROMP of norbornene using iPrPONOP MoCl3 as a precatalyst and (2-methoxybenzyl)magnesium chloride as a cocatalyst. This cocatalyst did not lend any improvements to the simpler nonchelating Grignard cocatalysts. The synthesis of a novel dialkyl zirconocene complex is also reported. The second and more heavily pursued endeavor was the development of longer-lived ruthenium olefin metathesis catalysts. Specifically, we aimed at improving the second-generation Hoveyda catalyst with the use of a hemilabile tridentate NHC ligand. Two novel catalysts bearing NHC ligands with a hemilabile ethoxy-pyridyl arm were synthesized along with their unique organic frameworks. The catalyst containing the 2,6-diisopropylphenyl group (C1-Me) was investigated more comprehensively because it was more readily prepared. This complex was characterized by high thermal stability under metathesis conditions and remarkable TONs in the self-metathesis of 1-decene. In our efforts to prepare C1-Me without utilizing a Grubbs I intermediate, a new complex (6) bearing our NHC ligand was isolated and characterized by 1H NMR and single crystal x-ray diffraction spectroscopy. The reaction of C1-Me with ethylene did not produce the desired C1-Me-methylidene variant - however, the same reaction with propylene gave C1-Me-ethylidene with relative ease. Analyzing the active catalytic species under the metathesis of 1-decene revealed that the resting state of the catalyst is not the expected methylidene, but rather the longer chain nonylidene. xi Initiation studies were conducted to compare the rates of initiation for catalyst C1-Me and the nonmethylated C1-H. First, the rate of metathesis was followed in the irreversible reaction with ethyl vinyl ether. Second, ligand exchange equilibrium experiments were carried out to compare the dissociation constants for the pyridyl moieties in both catalysts. The outcome of these studies revealed that catalyst C1-Me, with a methyl group in the phenoxide ring, exhibits a 10-fold increase in initiation versus the nonmethylated C1-H catalyst. The NHC ligand scaffold reported in this work may assist in the development of other inorganic and organometallic catalytic systems, as many rely on the use of ancillary ligands for support. Furthermore, fixing a hemilabile ethoxy-pyridyl arm onto already robust systems, such as ruthenium catalysts bearing a cyclic alkyl amino carbene ligand, may offer even greater catalytic turnover numbers (TONs).
