Molybdenum Carbene Complexes PDF Download
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Author: Matthew Frank Brown
Publisher:
ISBN:
Category :
Languages : en
Pages : 514
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Author: Matthew Frank Brown
Publisher:
ISBN:
Category :
Languages : en
Pages : 514
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Author: Mohasin Momin
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Category :
Languages : en
Pages :
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Author: Marcello Bertoli
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Category :
Languages : en
Pages : 146
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Author: Tamzyn Joyce Levell
Publisher:
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Category :
Languages : en
Pages : 286
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The synthesis and structure elucidation of fourteen novel Fischer ethoxy- and amino carbene complexes of molybdenum and chromium metals of the type [(CO)3L2M=C(X)R] were performed. Substitution of the parent pentacarbonyl complex [(CO)5M-C(OEt)(R)]; M = Mo, Cr; R = 2-thienyl, 2-furyl; with mono- and bidentate phosphine ligands yielded the corresponding tetracarbonyl complexes [(CO)4(PR’3)M-C(OEt)R] with M = Mo, Cr, R = 2-thienyl, 2-furyl and R’ = Ph, Cy or tricarbonyl complexes [(CO)3(DPPE)Mo-C(OEt)(2-furyl)], respectively. Aminolysis of these novel complexes resulted in substitution of the ethoxy substituent with an amino group. Full characterisation of these novel complexes included infrared spectroscopy, NMR (1H, 13C, 31P) spectroscopy, x-ray crystallography and mass spectral analyses. From the characterisation data, it was found that the cis isomer was dominant for the tetracarbonyl carbene complexes whereas the mer isomer was favoured in most cases for the tricarbonyl carbene complexes. Structural elucidation of nine of the novel complexes was confirmed with x-ray crystallography. The amino carbene complexes showed preference for a syn conformation of the oxygen atom of the furyl moiety and the nitrogen atom of the amino moiety in the crystal form. The ethoxy carbene complexes showed a preference for the anti conformation in the crystal form. The NMR analysis showed that resonance between the metal-carbene carbon-heteroatom stabilisation is more prevalent in the case of the amino carbene complexes. DFT calculations were performed for eleven of these complexes and their isomers. The infrared stretching modes were calculated and compared to experimental data. The HOMO and LUMO position and energy gaps were calculated. It was observed that the HOMO in all calculated complexes lay on the metal centre, while the LUMO was centred on the carbene carbon. It was found that the HOMO-LUMO gap was larger for the amino Fischer carbene complexes than for the ethoxy Fischer carbene complexes. From frontier orbital considerations, it is concluded that ligand substitution of carbonyls by phosphines as well as carbene substituent alterations does not seem to improve the reactivity of the novel complexes of this study particularly for the potential application as metathesis catalysts. The performed DFT calculations, in the future, can help determine which type of catalytic reactions these fourteen complexes would be most effective for.
Author: Gary W. Bentley
Publisher:
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Category :
Languages : en
Pages :
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Author: Carin E. Tattershall
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Category :
Languages : en
Pages :
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Author: Jayne E. Muir
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Category :
Languages : en
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Author: Valerie A. Osborn
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Category :
Languages : en
Pages :
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Author: Ross David Bemowski
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Category : Metal-metal bonds
Languages : en
Pages : 202
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Author: E.R. Braithwaite
Publisher: Elsevier
ISBN: 1483290891
Category : Science
Languages : en
Pages : 681
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Book Description
Molybdenum is an element with an extremely rich and interesting chemistry having very versatile applications in various fields of human activity. It is used extensively in metallurgical applications. Because of their anti-wear properties, molybdenum compounds find wide applications as lubricants - particularly in extreme or hostile environmental situations. Many molybdates and heteropolymolybdates are white and therefore used as pigments. In addition, they are non-toxic and act as efficient corrosion inhibitors and smoke suppressants. Hydroprocessing of petroleum is one of the largest industries employing heterogeneous catalysts. Molybdenum catalysts have shown great promise in the liquefaction of coal and this may develop into one of its most important catalytic uses. The use of molybdenum compounds in homogeneous catalysis is also significant. Three important classes of molybdenum compounds in the solid state are reviewed, viz., oxides, sulphides and halides. The role of molybdenum in inorganic catalysis and enzymes receives prominent mention because of their impact on the progress of science and technology. Further biochemical and enzymic factors are discussed in separate chapters and their reaction to agriculture and animal husbandry. A new classification of covalent compounds which abandons the traditional oxidation state concept allows a powerful approach to the organisation of the complex and rich chemistry of molybdenum. Dramatic colour diagrams of abundances of molybdenum compounds provide broad insights into the important features and trends in the chemistry of molybdenum including reactivity and mechanism. The book is intended for use mainly as a research monograph by the many workers who may encounter molybdenum chemistry or who are looking for its application and potential uses in different technological fields. However, it will also serve as an advanced text for university lecturers and postgraduate students interested in inorganic, physical and industrial chemistry, chemical technology or biochemistry and biotechnology.
