An experimental and theoretical investigation of unstable Fischer chromium carbene complexes
- Authors: Makanjee, Che Azad
- Date: 2013 , 2013-03-27
- Subjects: Chromium , Organolithium compounds , Carbenes (Methylene compounds) , Organometallic chemistry , Organometallic compounds , Organochromium compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4284 , http://hdl.handle.net/10962/d1002953 , Chromium , Organolithium compounds , Carbenes (Methylene compounds) , Organometallic chemistry , Organometallic compounds , Organochromium compounds
- Description: This organometallic study involves the use organostannanes and organolithiums as precursors to chromium Fischer carbene complexes. Fischer carbenes are typically electrophilic and are stabilized by a single π-donor substituent, and contain low oxidation state metals (often but not always from Group 6). They are highly reactive and can give access to a range of biologically active compounds through cyclopropanations, insertions, coupling and photochemical reactions. Synthesis and characterization of three MOM-protected α-alkoxy organostannanes was successfully carried out via a nucleophilic addition of tributylstannyllithium to suitable aldehydes, and immediate protection of the alcohol with MOM. Two N-BOC protected α-amino organostannanes were successfully synthesized and characterized via α-lithiation and tin-lithium exchange in the presence of TMEDA. Tin-lithium transmetallation of the organostannanes allowed access to the organolithiums required for the synthesis of novel Fischer carbenes. Addition of chromium hexacarbonyl to the organolithiums formed the acylpentacarbonyl chromate salt which was alkylated with Meerwein salt, resulting in the Fischer carbene and a by-product, tetrabutyltin, which proved difficult to remove. Several Fischer carbenes were synthesized and characterized, some simple and known and some novel. In silico work explored the reaction coordinate of the [2+2] cycloaddition towards the formation of β-lactams, and the photoactivation cycle that precedes this process. Computational work also showed the effect of the ligand on the stability and reactivity of the carbene. It was found that in some cases the oxygen on the ligand could negatively influence the stability of the carbene (when compared to a simple methyl carbene). A link between bond orders and back donation in Fischer carbenes was explored in an attempt to theoretically predict the stability of a range of carbenes. , Microsoft� Office Word 2007
- Full Text:
- Date Issued: 2013
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
Separation and characterisation of chromium (III) carboxylate solutions
- Authors: Bryson, Michael Andrew Walker
- Date: 1981
- Subjects: Chromium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4416 , http://hdl.handle.net/10962/d1006847
- Description: From Summary: The complexes present in chromium(III) carboxylate solutions (acetate or formate) were separated using ion exchange chromatography, electrophoresis and gel filtration. Eight cationic species and one non-ionic species with charges from 0 to +3 and nuclearities ranging from mononuclear to quadranuclear were isolated from chromium(III) acetate solutions. Six cationic species with charges from +1 to +3 and nuclearities ranging from mononuclear to trinuclear were isolated from chromium(III) formate solutions. The empirical formulae for these complexes were determined by analytical methods. Infra- red spectroscopy was used to distinguish between monodentate and bidentate bridged carboxylate ligands. An immediate change in the visible spectrum of a complex on its acidification was used as evidence that a terminal hydroxo group was present.
- Full Text:
- Date Issued: 1981
A comparative kinetic study of the reaction between chromium nitrate solutions and the carboxyl groups of acetate and collage
- Authors: Russell, Allan Edward
- Date: 1962
- Subjects: Chemical kinetics , Chromium , Spectrophotometry , Electrophoresis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4493 , http://hdl.handle.net/10962/d1013101
- Description: The kinetics of the coordination reaction between the carboxyl group of the acetate radical and the trivalent chromium ion has been examined by independent methods at a temperature selected to yield reasonably accurate rate data. The study has been extended to an examination of the rate of chromium "fixation" by the carboxyl groups of hide collagen in a series of miniature tannages carried out under similar conditions for comparative purposes. The effect of olation of the chromium ions in solution on the kinetics of t he coordination reaction has also been examined. The rate of coordination of the acetate radical was followed by solvent extraction and spectrophotometric techniques over a range of concentration and pH levels. The rate data revealed a reaction having typical mass-action characteristics, the rate of reaction depending on the concentration levels of the chromium ion and the ionised acetate radical. An attempt made to distinguish a differential reaction rate in the case of a parallel reaction series using boiled and aged chromium nitrate reactant solutions, failed to reveal any significant differences between the series. The reactant solutions gave absorption spectra characteristic of the trivalent chromium ion with maxima in the 420 mµ and 570 mµ wavelength regions. The changes in optical density occurring in the vicinity of the maxima were followed spectrophotometrically, the height of the 570 mµ being found to increase during the course of reaction, while the height of the 420 mµ peak decreased. The variation in optical density at the 570 mµ peak was found to be directly related to the increase in concentration of the product complex in solution in accordance with the Baer-Bougher law, while the decrease in the height of the 420 mµ peak was related to the properties of unolated OH groups associated with the chromium complex as governed by pH and olation changes during the course of reaction. Boiled and aged chromium nitrate solutions gave reactant solutions having initial optical densities greater than those of the correspending fresh reactant solutions at the 570 mµ peak, and less than those of the fresh solutions at the 420 mµ peak. During the course of reaction, however, the two series converged to the same values. The equilibrium reaction solutions were subjected to paper electrophoretic study which indicated that all tho chromium was present in the form of cationic species. This finding was in accordance with stoicheiometric indications in the solvent extraction studies where coordination in a l : 1 ratio was reflected, giving rise to positively charged complex ions only. Making due allowance for band spreading the numbers of species predicted from the kinetic studies correspond with the electrophoretic patterns found. Application of the classical second order kinetic expression to the solvent extraction rate data, yielded plots having two distinctly linear sections, apparently indicating consecutive second order processes occurring in solution, contrary to the findings of previous workers who assign a first order mechanism to the reaction. This finding was consistent with the view that in the case of both the fresh and aged series, reaction consisted of successive coordination of an acetate radical to each chromium atom of a diol complex. Second order rate "constants" were calculated for each step and their dependency on pH level demonstrated. The findings of Hamm et al that these were first order reactions independent of acetate co'ncentration are believed to be due to their use of a large excess of acetate in their experiments. The kinetic study was further extended to an examination of the rate of "fixation"of trivalent chromium by the carboxyl groups of hide collagen under comparable conditions in a series of miniaturv tanning experiments in which the tannage substrate was provided in each of two physical forms:- (a) As hide powder where surface development was large, and (b) as prepared pelt pieces in which the fibrous weave pattern was retained. In view of the heterogeneity of the tannage systems, remarkable similarity was observed in the reaction course when compared with that of the acetate coordination studies, particularly in the case of the hide powder tannages. The dependency of the tannage rate data upon concentration and pH conditions was also found to be the same as in the case of the pure chemical system. The exact correlation between the rate data for the tannage and pure chemical systems was demonstrated by means of correlation plots. Close correlation was revealed in the case of hide powder tannage while the smaller degree of correlation observed in the case of the pelt tannage systems was attributed to the modifying effects of diffusion, particularly on the initial reaction velocity. The effect of using boiled and aged chromium solutions in the tannages was to increase the initial rate of chroniill!l "fixation" apparently due to tho coordination of a dial species at each coordination site. After the initial reaction period, the two series showed a tendency to converge as in the case of the spectrophotometric studies on the acetate reaction. The convergence trend was regarded as indicative of the tendency for the chromium in fresh solutions to under go rapid olation to the ame level as in the boiled and aged solutions. The experimental observations made on the various systems lead to the following conclusions:- (a) The mechanism of coordination of the acetate radical ttrivalent chromium appears to involve the successive coordination of ligand to each of the chromium atoms of a diol complex, both coordination steps proceeding by second order reaction mechanisms. (b) At the pH levels at which the reaction is carried out, the formation of elated bodios is rapid so that reaction in the case of both fresh and aged solutions essentially occurs between an elated species and the ionised acetate radical. (c) Modificati0ns in the absorption spectrum of the reactant solution at the 570 mµ peak are directly related to coordination, while changes at the 420 mµ peak are related to the formation of loosely-bound hydroxo chromium compounds, the concentrations of which depend on the pH level. (d) The mechanism of chromium fixation in hide is essentially similar to that operating in the case of coordination of the acetate radical to chromium, involving attachment of chromium to the side chain acid r sidues of collagen. (e ) The effect of olation is to enhance the rate of chromium fixation by hide protein during the initial reaction stages and to render possible bridge formation between adjacent side chains by secondary coordination during the latter reaction stages. (f) Where pelt pieces are used instead of hide powder, the initial rate of chromium fixation is dominated by the rate of diffusion of chromium into the fibrous structure. It should be stressed that the observations made on the various reaction systems cannot be regarded as exhaustive and the conclusions are subject to further confirmation. Consequently, the present study is essentially of a preliminary nature, but it is felt that the need for further investigation along similar lines has been demonstrated.
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- Date Issued: 1962
Studies in chromium complexes
- Authors: Friend, Maurice Temple
- Date: 1953
- Subjects: Complex ions , Chromium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4474 , http://hdl.handle.net/10962/d1011892 , Complex ions , Chromium
- Description: In this work physical and analytical methods have been used to investigate the potassium salts of certain dioxalato chromium (III) complexes. The solid potassium salts of the trioxalatochromiate and the cis and trans dioxalatodiaquochromiates together with a salt corresponding to potassium dioxalatosulphatoaquochromiate were prepared. The mono- and dihydroxo derivatives of the cis and trans dioxalatochromiates were also obtained in aqueous solution. The methods of preparation and analysis used are described. Spectrophotometric absorption curves obtained on solutions of these salts using a Beckman Spectrophotometer are in agreement with results of previous workers, and the new absorption curve obtained from a solution of the solid cis dioxalatodiaquochromia salt shows that it is pure and gives additional proof of the completeness of the trans - cis isomerisation. Summary, p. i.
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- Date Issued: 1953
Studies in chromium complexes
- Authors: Cooper, Desmond Rudolph
- Date: 1953
- Subjects: Chromium , Complex ions
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4523 , http://hdl.handle.net/10962/d1014707
- Description: The chemistry of co-ordination compounds in general has played an important role in the development of the modern theory of valency, but the properties of complex salts between chromium and organic compounds containing carboxyl and amino- groups are of additional interest because of their bearing on the theory of certain technological processes such as chromium plating and, in particular, chrome-tanning. Owing to the rapid development of valence theory over the last two decades the technological chemist finds himself at a disadvantage vis-a-vis his academic counterpart in attempting to interpret the results of researches relating to these compounds as he must rely on the less powerful "classical" approach to his problems. Hence the need was felt for a brief survey of modern concepts of valency in terms of wave mechanics. For a more extended study the reader may consult the appropriate references and text books.
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- Date Issued: 1953
An investigation of certain complex ions of trivalent chromium by spectrophotometric and other physical methods
- Authors: Burley, Ralph Walter
- Date: 1950
- Subjects: Chromium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4521 , http://hdl.handle.net/10962/d1014675
- Description: Although chromium coordination compounds are of considerable technological importance, they have been subjected to few thorough investigations since Werner's original experlments, in spite of the fact that we now possess a number of accurate physical methods, not available in Werner's time for the study of coordination complexes, The object of the work described in this thesis was to obtain further information on the chemistry of complex chromium(III) ions with special reference to the dioxalato-diaquochromiate system, [Cr(C₂0₄)₂(H₂0)₂]. For this purpose; spectrophotometric and potentlometrlc measurements were combined to yield information on a number of topics, The spectrophotometric investigations consisted in measuring the absorption spectra of the potassium salts of the complexes under consideration and in observing the changes in light absorption which occur during their formatlon and decomposition. The instrument used was a Beckmann Quartz Spectrophotometer model du. More than than twelve new absorption spectra were measured in this work and in conjunction with the spectra of other chromium and cobalt complexes reported by earlier workers, these are used to review the position of spectrophotometry as a method of investigating chromium complexes. The reasons for the shapes of the absorption spectra are discussed and it is concluded that spectrophotometry is useful for observing the progress of reactions involving complex ions and for analysing solutions, but that more fundamental data cannot be expected from the absorption curves.
- Full Text:
- Date Issued: 1950
The construction of a precision conductance bridge and its application to a study of chromium sulphate complexes
- Authors: Goddard, Errol Desmond
- Date: 1949
- Subjects: Chromium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4476 , http://hdl.handle.net/10962/d1012038 , Chromium
- Description: A constant temperature room employing the comparatively new method of temperature control by means of a thyratron relay has been constructed. A high precision conductance bridge has been built in a very convenient form. Improvements include the incorporation of a cathode ray oscilloscope as null detector and the inclusion of a very stable oscillator of the phase shift type which is capable of giving a very pure wave form. Tests carried out on a system of degenerative tuning showed the the system is not easily applicable to high gain amplifiers. A new form of conductometric titration cell, employing the dipping type electrodes has been designed with special precautions against possible Parker Effect. A series of tests has been carried out on three types of cell to ascertain the effects of absorption, polarisation and Parker Effect on the accuracy of an ordinary conductometric titration. Conductometric titrations of NaOH solutions of violet and green chromic sulphate has been carried out, and the effect of aging these solutions closely studied. In addition, conductometric titrations of BaCL₂ into the chromic solutions have been made, and the NaOH titrations have been studied potentiometrically as well.
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- Date Issued: 1949