Binuclear mixed biscarbene complexes of bithiophene were synthesized via the classical Fischer method of synthesis. The metal carbonyls, Mo(CO)6, Cr(CO)6, W(CO)6 and Mn(MeCp)(CO)3 were reacted with dilithiated bithiophene to afford complexes of the formula, [M(CO)5{C(OEt)C4H2S-C4H2SC(OEt})M'(CO)5] (in case of manganese, M(CO)5 is replaced with MMeCp(CO)2), where [M] and [M'] are the metal carbonyls in different combinations. Quenching was achieved with triethyl oxonium tetrafluoroborate. In all the reactions the products included monocarbene complexes, biscarbene complexes and the decomposition products. C-C coupling reactions produced unexpected biscarbene complexes of Cr, W, and Mo having extended bithiophene spacers. The complexes were of the formula,
[M(CO)5{C(OEt)C4H2S-C4H2SC(R)-C(R)C4H2S-C4H2SC(OEt})M'(CO)5] (R = O, OH or OEt).
These complexes were characterized with NMR, infrared spectroscopy and some with mass spectrometry. Furthermore, three biscarbene complexes of the metal combinations Mo(CO)6 and Cr(CO)6, W(CO)6 and Cr(CO)6, and Mn(MeCp)(CO)3 and Cr(CO)6 were all reacted with 3-hexyne. The result was the benzannulation or the Dötz products. / Chemistry / M. Sc. (Chemistry)
| Identifer | oai:union.ndltd.org:netd.ac.za/oai:union.ndltd.org:unisa/oai:uir.unisa.ac.za:10500/1208 |
| Date | 30 November 2005 |
| Creators | Ramontja, James |
| Contributors | Landman, Marilé |
| Source Sets | South African National ETD Portal |
| Language | English |
| Detected Language | English |
| Type | Dissertation |
| Format | 1 online resource (83 leaves) |
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