Quantum Mechanical Studies of the Mechanisms of Some Transition Metal Organometallic Reactions

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The mechanistic pathways of three organometallic reactions, namely the oxidation of ethylene by chromyl chloride leading to the formation of epoxide, 1,2-dichloroethane, 1,2-chlorohydrin, acetaldehyde, and vinyl alcohol precursors; the olefin metathesis reaction involving ethylene and 20 metal methylidene Cl4MCH2(M=Cr, Mo, W, Ru, Re) and metal oxo-methylidene Cl2(O)MCH2(M=Cr, Mo, W, Ru, Re) complexes; and the transition-metal-assisted formation of 1,2-dinitroso complexes of cobalt and its congeners have been studied using hybrid density functional theory at the B3LYP/LACVP* level of theory. The formation of the epoxide precursor (Cl2(O)Cr-OC2H4) was found to take place via initial [2+2] addition of ethylene across the Cr=O bond of CrO2Cl2 to form a chromaoxetane intermediate, as opposed to [3+2] addition across the two Cr=O bonds of CrO2Cl2 as suggested in earlier studies. The hitherto unexplored pathway involving initial [3+2] addition of ethylene across the Cr=O and Cr-Cl bonds of CrO2Cl2 was found to be more favorable than the [3+2] addition across the two Cr-O bonds of CrO2Cl2. The formation of the 1,2-dichloroethane precursor was found to take place via [3+2] addition of ethylene across the two Cr-Cl bonds of CrO2Cl2. The 1,2-chlorohydrin precursor was also found to originate from [3+2] addition of ethylene across the Cr-O and Cr-Cl bonds of CrO2Cl2 as opposed to [2+2] addition of ethylene across the Cr-Cl bond. Also the vinyl alcohol and acetaldehyde precursors were found to arise from a direct attack of one of the carbon atoms of ethylene on an oxygen atom of CrO2Cl2 through a triplet intermediate. In the reactions of Cl4MCH2(M=Cr, Mo, W, Ru, Re) with ethylene it was found that the formation of the metallacyclobutane through formal [2+2] cycloaddition, a key step in the olefin metathesis reaction according to the Herrison-Chauvin mechanism, is a low-barrier process in each of the complexes studied. It was also found that the active species for the formation of the metallacyclobutane is a carbene complex and not a carbenoid complex. One key factor was found to be responsible for the difference in metathesis activity in these complexes: the stability of the carbenoid complexes relative to the carbenes. In Cr and Ru, the carbenoid complexes are more stable than the carbenes and thus Cl4CrCH2 and Cl4RuCH2 are likely to exist in the lower- 21 energy carbenoid Cl3MCH2Cl form as opposed to the carbene Cl4M=CH2 form. This is likely to deplete the reaction surface of the active species of the process, making Cl4MCH2(M=Cr, Ru) not suitable for olefin metathesis. This suggests that whereas Cl4MCH2 (M = Mo, W, Re) may catalyze olefin metathesis, Cl4MCH2 (M = Cr, Ru) may not. The W and Re complexes have been found to have greater metathesis activity than the Mo complex. In the Cl2(O)MCH2 (M=Mo, W, Re) complexes the metathesis reaction has favorable energetics and is found to be more feasible than the side-reactions studied while in the Cl2(O)MCH2(M=Cr, Ru) complexes, the olefin metathesis is found to be less favorable than the side reactions. In the transition-metal-assisted formation of 1,2-dinitrosoalkanes, it was found that the activation barriers for the one-step [3+2] addition pathway for the formation 1,2-dinitrosoalkanes are generally very low while the activation barriers for the [2+2] addition of the C=C bond of the olefins across the M-N bonds of CpM(NO)2 (M=Co, Rh, Ir) to form an intermediate are generally very high. A transition state for the re-arrangement of the products of [2+2] addition to the products of [3+2] addition could not be located, indicating that the re-arrangement of the products of [2+2] addition by reductive elimination involving the second metal-nitrogen π-bond to form the observed 1,2-dintrosoalkanes as suggested in the work of Rappé and Upton may not be possible. Therefore it is concluded that the direct one-step [3+2] addition pathway proposed by Bergman and Becker for the formation of 1,2-dinitrosoalkanes is a more plausible pathway.
A thesis submitted to the Department of Chemistry, College of Science, Kwame Nkrumah University of Science and Technology, Kumasi in partial fulfillment of the requirements for the degree of Doctor of Philosophy