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)

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)

A series of Fischer mono- and biscarbene complexes of the type [MLn{C=(XR)R'}] was synthesized and characterized. The redox behavior of the complexes was studied by different techniques, including cyclic voltammetry, spectroelectrochemistry, ESR and computational methods. Different transition metals (M) and carbene substituents (XR, R') were employed to compare both the effect of the central metal atom as well as the carbene substituent. Thienyl, furyl and ferrocenyl chromium(0) mono- and biscarbene complexes with ethoxy and amino substituents were electrochemically studied in CH2Cl2. Results were mutually consistent with computational data showing that the carbene double bond of all complexes is reduced pseudo reversibly to an anion radical, -Cr-C•. The Cr centers are oxidized in two successive one electron transfer steps to Cr(II) via the Cr(I) intermediate. For all ferrocenyl carbene complexes the Fe(II) is oxidized after the first oxidation of Cr. It was found that with respect to the aryl substituents the donating effect decreases from Fc>Fu>Th. Stabilization from the XR substituent, where XR = NHR, also resulted in lower redox potentials compared to their OEt analogues. The inclusion of ferrocene in the carbene substituent was done, as its redox activity and increased donating effect are well known. Mono- and biscarbene complexes with ethoxy and amino substituents of both chromium and tungsten were electrochemically studied. Again experimental data were supported by computational studies. Similar to the ethoxy chromium complexes, reduction of the W=C fragment to -W-C• was observed. However oxidation of the Fc group occurred first before the electrochemically irreversible oxidation process for W(0) involving a three electron-mediated process as seen in chronocoulometric analyses. The tungsten oxidation was restricted to a W0/II, consistent with computational studies, by the use of the electrolyte [NnBu4][B(C6F5)4]. The short-lived W(II) species were calculated to be stabilized by agostic CH···W interactions, similar to the chromium analogues. To extend linkers between the metal-carbene termini and investigate metal-metal interaction, biferrocenyl and 2,5-thienylbiferrocenyl tungsten(0) mono-and biscarbene complexes were synthesized and studied by spectroelectrochemistry. A metal-metal charge transfer transition between the tungsten carbonyl increment and the biferrocenyl / 2,5-thienylbiferrocenyl unit was confirmed by infrared spectroelectrochemical studies. The electronic interaction in the corresponding cationic species can be described as weakly coupled class II systems according to Robin and Day. The cymantrenyl moiety, Mn(η5-C5H4)(CO)3, provides an interesting alternative to ferrocene as an organometallic molecular tag, however the instability of the radical cation impairs its use. Improved stability of the cation, monitored by electrochemical measurements, was accomplished by substituting a carbonyl with a ferrocenyl Fischer carbene ligand resulting in Mn(I) oxidation occuring at lower potentials than ferrocenyl oxidation. These uncommon Fischer carbene complexes is the first organometallic multi-tags reported. The mono cationic species, [CpMn(CO)2{=C(OEt)Fc}][PF6], could be isolated and characterized with ESR analysis. Finally, transmetallation from the tungsten(0) Fischer carbene complexes yielded examples of rare acyclic alkoxy- and aminocarbene complexes of gold(I). Single x-ray structures for all complexes could be obtained including the novel ferrocenophane dinuclear biscarbene Au(I) complex. All structures display unsupported aurophilic interactions, while the bridging biscarbene shows a semi-supported Au-Au interaction. In the case of the furanyl/thienyl methoxy monocarbene complexes, extended Au-Au interactions result in oligomeric structures. Although this study is of a fundamental nature, it is imperative for the understanding and design of gold compounds with specific applications. / Thesis (PhD)--University of Pretoria, 2013. / gm2014 / Chemistry / unrestricted