Mahungu, Symon Maina (1987) A Study of the Reactions of the Halocarbonyls. Mo (Co) 4X2 (X = Cl. Br) With Various Alkyl Amines. Masters thesis, Kenyatta University.
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Abstract
This thBsis describes the reactions of dihalotetracarbonylmolybdenum (II), Mo(CO)4X2 eX=Cl.Br). complexes with various alkrl amines. The aim of the project was to find out whether these halocarbonyls react via a solvolytic or a redoxy mechanism with alkylamines. The highly reactive halocarbonyls, MoeCO)4x2' were prepared following literature methods. These halocarbonyls reacted with neat piperidine giving the zerovalent molybdenum complex. tetracarbonylbis(piperidine)molybdenum(O),Mo(CO)4(CSHIONH)2· The amine salt,CsH10NH.HX, for the respective halogen was isolated. The NMR spectrum of the basic distillate from the reaction mixture showed a singlet signal at ~=6.lppm which is '.itnh'e olefinic region. The signal was not affected by deuterating the distillate with deuterated water. When the reaction was carried out using either tetrahydrofuran (T.H.F.) or methanol which had been cooled in dry-ice/acetone mixture as solvents, tHe same products as those mentioned above were optained. Treatment of the halocarbonyls, Mo(CO)4X2 (X~Cl,Br), with neat butylamine or propylamine which had been cooled in dry-ice/acetone mixture gave the trisubstituted zerovalent molybdenum'complexes,Mo(CO)3L3 (L = butylamine, propylamineJ. The NMR spectrum .of each .basic distillate from t h e s n reaction mixtures showed a singlet signal at ~= 5.B ppm for butylamine reaction and at ~=5.3 ppm for propylamine reaction. The s e singletsigilaIs are i ntheolefinic region thus showing that the amines have been dehydrogenated. These signals were not affected by deuterating the distillates with deuterated water. The zerovalent molybdenum complex, tris (but Y I amine )tri carbonyImol y b den uIII ( 0 )" was also is 01 ated when the h~locarbonyl, Mo(CO)4Br2" was treated with butylamine/methanol mixture. This mixture had been cooled in dry ice/acetone mixture before being added onto the halocarbonyl, Mo(CO)4Br2. The infrared spectra of the zerovalent molybdenum complexes have been studied. Various assignments for the carbonyl stretching modes have been mad~, The N-H stretching frequency of the coordinated amine was found to be significantly lower than th~t for th~ free ~min8. A careful analysis of the NMR spectra shows that pipe rid interacts with the haIoCorbon y Is: M 0 (C 0 )4 X 2 forming 1,4,5,6-tetrahydroanabasine. The high reactivity of the enamines formed from butylamine and propylamine made it impossible to isolate any identifiable organic products. Th8 present works SllOWIl Lh e t tile halo carbonyls,~10 ( CO) 4X2 (X = C1, [l r ) r 0 act wit 11 a,1kYla III in e s via a redoxy mechanism.
| Item Type: | Thesis (Masters) |
|---|---|
| Subjects: | Q Science > QD Chemistry |
| Divisions: | Africana |
| Depositing User: | Geoffrey Obatsa |
| Date Deposited: | 27 Apr 2017 11:43 |
| Last Modified: | 27 Apr 2017 11:43 |
| URI: | http://thesisbank.jhia.ac.ke/id/eprint/1515 |
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