The synthesis of α-alkoxy and α-aminostannanes as precursors to Novel Chromium Fischer Carbenes
- Authors: Meyer, Annalene
- Date: 2012
- Subjects: Alkoxides , Organometallic compounds , Carbenes (Methylene compounds) , Chromium , Molybdenum , Tungsten , Organolithium compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4371 , http://hdl.handle.net/10962/d1005036 , Alkoxides , Organometallic compounds , Carbenes (Methylene compounds) , Chromium , Molybdenum , Tungsten , Organolithium compounds
- Description: The present study involves the use of main group organometallics: organostannanes and organolithiums as precursors to chromium Fischer carbene complexes. Fischer carbenes are well stabilized by the π‐donor substituents such as alkoxy and amino groups and low oxidation state metals such as Group 6 (Chromium, Molybdenum or Tungsten). Carbenes are an important intermediate in the synthesis of a range of compounds through cyclopropanations, insertions, coupling and photochemical reactions. Synthesis and successful characterisation of three α‐alkoxystannanes was achieved via nucleophilic addition of tributylstannyllithium to the respective aldehydes, followed by an immediate MOM protection of the resulting alcohol. Six α‐aminostanannes were synthesised, consisting of N‐BOC, N‐acetyl and N‐ethyl derivatives of pyrrolidine and piperidine, via α‐lithiation and subsequent tinlithium transmetallation in the presence of TMEDA. The ¹³C NMR analysis highlighted an interesting phenomenon of tin‐carbon coupling that revealed unique structural information of both types of stannanes. DFT analysis was completed on the series of stannanes; a predicted frequency analysis was obtained which complemented the experimental Infra‐red data in elucidation of the compounds. The α‐alkoxy and α‐aminostannanes provided stable precursors to the organolithiums required for the synthesis of the novel Fischer chromium carbenes. The organolithiums were obtained via tinlithium exchange at low temperatures, followed by the addition of chromium hexacarbonyl to form the acylpentacarbonyl‐chromate salt. Alkylation of this intermediate using a Meerwein salt, Me₃OBF₄, gave rise to the novel Fischer chromium carbene complexes. Fischer chromium carbenes derived from the two isomeric butyl and isobutyl stannanes and the two N‐ethyl α‐aminostannanes were successfully synthesised. The difficulty encountered in the purification of the Fischer carbene complexes hindered the full characterisation, due to the presence of a by‐product, tetrabutyltin.
- Full Text:
- Date Issued: 2012
- Authors: Meyer, Annalene
- Date: 2012
- Subjects: Alkoxides , Organometallic compounds , Carbenes (Methylene compounds) , Chromium , Molybdenum , Tungsten , Organolithium compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4371 , http://hdl.handle.net/10962/d1005036 , Alkoxides , Organometallic compounds , Carbenes (Methylene compounds) , Chromium , Molybdenum , Tungsten , Organolithium compounds
- Description: The present study involves the use of main group organometallics: organostannanes and organolithiums as precursors to chromium Fischer carbene complexes. Fischer carbenes are well stabilized by the π‐donor substituents such as alkoxy and amino groups and low oxidation state metals such as Group 6 (Chromium, Molybdenum or Tungsten). Carbenes are an important intermediate in the synthesis of a range of compounds through cyclopropanations, insertions, coupling and photochemical reactions. Synthesis and successful characterisation of three α‐alkoxystannanes was achieved via nucleophilic addition of tributylstannyllithium to the respective aldehydes, followed by an immediate MOM protection of the resulting alcohol. Six α‐aminostanannes were synthesised, consisting of N‐BOC, N‐acetyl and N‐ethyl derivatives of pyrrolidine and piperidine, via α‐lithiation and subsequent tinlithium transmetallation in the presence of TMEDA. The ¹³C NMR analysis highlighted an interesting phenomenon of tin‐carbon coupling that revealed unique structural information of both types of stannanes. DFT analysis was completed on the series of stannanes; a predicted frequency analysis was obtained which complemented the experimental Infra‐red data in elucidation of the compounds. The α‐alkoxy and α‐aminostannanes provided stable precursors to the organolithiums required for the synthesis of the novel Fischer chromium carbenes. The organolithiums were obtained via tinlithium exchange at low temperatures, followed by the addition of chromium hexacarbonyl to form the acylpentacarbonyl‐chromate salt. Alkylation of this intermediate using a Meerwein salt, Me₃OBF₄, gave rise to the novel Fischer chromium carbene complexes. Fischer chromium carbenes derived from the two isomeric butyl and isobutyl stannanes and the two N‐ethyl α‐aminostannanes were successfully synthesised. The difficulty encountered in the purification of the Fischer carbene complexes hindered the full characterisation, due to the presence of a by‐product, tetrabutyltin.
- Full Text:
- Date Issued: 2012
Molybdeunum mineralization with emphasis on porphyry systems genesis and exploration
- Authors: Puig-Pichuante, R M
- Date: 1986
- Subjects: Molybdenum , Porphyry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5023 , http://hdl.handle.net/10962/d1006840
- Description: Mo became very important in the last century, because of its sophisticated properties and its use in the new technology of alloys . Porphyry systems (porphyry Cu-Mo and Mo) contribute a significant proportion (90 - 95 per cent) to the Mo world's production. This type of deposit is associated mainly with Phanerozoic orogenic belts. Above 87per cent of the world resources are in the American Circumpacific belts , both Andean and Cordilleran . Ore grade in porphyry Cu-Mo range from 0,005 to 0,04per cent Mo, whereas in porphyry Mo grades range from 0,08 to 0,75per cent Mo . These deposits are associated with a magmatism which shows an evolution from calcic in island arcs, to calc-alkaline in magmatic back arcs, with an increase of the Mo content in the same direction. Porphyry Mo deposits display several features in common with porphyry Cu deposits. hydrothermal Similarities include nature of host alteration patterns and distribution of rock intrusives, ore minerals. An interesting difference is found in the Re contents of the molybdenite mineral. This element is higher in the molybdenites of porphyry Cu, than in those of the porphyry Mo. The ore genesis process begins involves partial melting, within enriched zones of the upper mantle and magma differentation, liquid state thermogravitational diffusion, magma convection and boiling. These processes progressively concentrate Mo in the fluids, which are released at some stage, into sulphidic hydrothermal systems, under complex geologictectonic conditions involving fracturing, brecciation and hydrothermal alteration. Major concentrations of the ore mineral are always associated with potassic alteration, and with late magmatic-early hydrothermal stages (Chilean and Western North American porphyries). Geological mapping and a close understanding of alteration and mineralization patterns, and lithogeochemistry are important tools for the exploration of porphyry Mo deposits. Geochemical prospecting, using soils, vegetation and water as sampling media, and regional aeromagnetic, gravity surveys, aerial photography and remote sensing, are us.
- Full Text:
- Date Issued: 1986
- Authors: Puig-Pichuante, R M
- Date: 1986
- Subjects: Molybdenum , Porphyry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5023 , http://hdl.handle.net/10962/d1006840
- Description: Mo became very important in the last century, because of its sophisticated properties and its use in the new technology of alloys . Porphyry systems (porphyry Cu-Mo and Mo) contribute a significant proportion (90 - 95 per cent) to the Mo world's production. This type of deposit is associated mainly with Phanerozoic orogenic belts. Above 87per cent of the world resources are in the American Circumpacific belts , both Andean and Cordilleran . Ore grade in porphyry Cu-Mo range from 0,005 to 0,04per cent Mo, whereas in porphyry Mo grades range from 0,08 to 0,75per cent Mo . These deposits are associated with a magmatism which shows an evolution from calcic in island arcs, to calc-alkaline in magmatic back arcs, with an increase of the Mo content in the same direction. Porphyry Mo deposits display several features in common with porphyry Cu deposits. hydrothermal Similarities include nature of host alteration patterns and distribution of rock intrusives, ore minerals. An interesting difference is found in the Re contents of the molybdenite mineral. This element is higher in the molybdenites of porphyry Cu, than in those of the porphyry Mo. The ore genesis process begins involves partial melting, within enriched zones of the upper mantle and magma differentation, liquid state thermogravitational diffusion, magma convection and boiling. These processes progressively concentrate Mo in the fluids, which are released at some stage, into sulphidic hydrothermal systems, under complex geologictectonic conditions involving fracturing, brecciation and hydrothermal alteration. Major concentrations of the ore mineral are always associated with potassic alteration, and with late magmatic-early hydrothermal stages (Chilean and Western North American porphyries). Geological mapping and a close understanding of alteration and mineralization patterns, and lithogeochemistry are important tools for the exploration of porphyry Mo deposits. Geochemical prospecting, using soils, vegetation and water as sampling media, and regional aeromagnetic, gravity surveys, aerial photography and remote sensing, are us.
- Full Text:
- Date Issued: 1986
A critical study of the determination of molybdenum in plant material
- Authors: Gore, William Tompson
- Date: 1961
- Subjects: Molybdenum , Plants -- Analysis , Spectrophotometry , Polarography
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4477 , http://hdl.handle.net/10962/d1012071 , Molybdenum , Plants -- Analysis , Spectrophotometry , Polarography
- Description: 1. Polarographic and spectrophotometric methods for the determination of molybdenum were reviewed. 2. The inclusion of salicylaldoxine in several supporting electrolytes was examined with a view to developing a polarographic procedure, suitable for routine analyses, which did not necessitate a preliminary time-consuming separation stage. A stable molybdenum wave was obtained from an electrolyte having a composition similar to the test solution obtained after the wet digestion of plant material. The height of the wave was found to be, over an optimum range, independent of the reagent concentrations. The wave was however distorted by a maximum, which rendered it unsuitable for quantitative analytical application. 3. The spectrophotometric procedure for molybdenum using thiocyanate is virtually specific and was examined critically. Modifications were found to improve the sensitivity of the procedure, and the stability of the chromatic compound. 4. The modified spectrophotometric procedure is recommended for the routine determination of molybdenum in plant material.
- Full Text:
- Date Issued: 1961
- Authors: Gore, William Tompson
- Date: 1961
- Subjects: Molybdenum , Plants -- Analysis , Spectrophotometry , Polarography
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4477 , http://hdl.handle.net/10962/d1012071 , Molybdenum , Plants -- Analysis , Spectrophotometry , Polarography
- Description: 1. Polarographic and spectrophotometric methods for the determination of molybdenum were reviewed. 2. The inclusion of salicylaldoxine in several supporting electrolytes was examined with a view to developing a polarographic procedure, suitable for routine analyses, which did not necessitate a preliminary time-consuming separation stage. A stable molybdenum wave was obtained from an electrolyte having a composition similar to the test solution obtained after the wet digestion of plant material. The height of the wave was found to be, over an optimum range, independent of the reagent concentrations. The wave was however distorted by a maximum, which rendered it unsuitable for quantitative analytical application. 3. The spectrophotometric procedure for molybdenum using thiocyanate is virtually specific and was examined critically. Modifications were found to improve the sensitivity of the procedure, and the stability of the chromatic compound. 4. The modified spectrophotometric procedure is recommended for the routine determination of molybdenum in plant material.
- Full Text:
- Date Issued: 1961
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