Barron, Andrew R.2009-06-042009-06-042001Borovik, Alexander Sergeevich. "Aluminum and gallium chloride stabilized arene-mercury complexes." (2001) Diss., Rice University. <a href="https://hdl.handle.net/1911/17942">https://hdl.handle.net/1911/17942</a>.https://hdl.handle.net/1911/17942Reaction of HgCl2 with two equivalents of MCl3 in an aromatic solvent yields Hg(arene)2(MCl4) 2 where arene = C6H5Me, C6H5Et, o-C6H4Me2, C6H3 -1,2,3-Me3, M = Al, Ga. Reaction of HgCl2 with MCl3 in benzene, m-xylene, and p-xylene results in the formation of liquid clathrates whose spectroscopic characterization is reported. In the solid state, all compounds, with the exception of o-xylene complexes, exist as neutral complexes in which two arenes are bound to the mercury and the MCl3 groups are bound through bridging chlorides to the mercury. o-xylene complex exists as a cation anion pair [Hg(o-C6H4Me 2)2(AlCl4)][AlCl4]. However, in solution all mercury-arene compounds exist as neutral complexes. The structures of Hg(arene)2(AlCl4)2 and [Hg(arene)2(AlCl 4)]+ have been optimized by DFT calculations to facilitate the assignment of the 13C CPMAS NMR spectra, and are in good agreement with the X-ray diffraction structures. Dissolution of Hg(arene)2(MCl4)2 in C6D6 results in a rapid H/D exchange and the formation of the appropriate dn-arene and C6D5H. H/D exchange between excess arene and C6D6 is also found to be catalyzed by Hg(arene)2(MCl4)2 including those with a different arene ligand. Based on DTF calculations the inter- and intra-molecular mechanism of the exchange is proposed. Mercury-arene complexes are found to be very active catalysts for the alkylation of arenes by olefins. Ethylene, propylene, and cyclohexene reacts with benzene or toluene to form mono- and polyalkylated products, the distribution being dependent on the nature of olefin. Based on the deuterium labeling experiments two different mechanisms of arene alkylation are discussed. Reaction of K[CpFe(CO)2] with a large excess of GaCl 3 yields [{CpFe(CO)2}Ga(Cl&middot;GaCl3)(mu-Cl)] 2, while reactions with 1 and 0.5 equivalents yields [{CpFe(CO) 2}GaCl2]n, and [{CpFe(CO)2}2Ga(mu-Cl)] infinity, respectively. [{CpFe(CO)2}GaCl2] n reacts with MeCN to yield [CpFe(CO)2]GaCl2(MeCN). Reduction of [{CpFe(CO)2}2Ga(mu-Cl)]infinity with potassium in Et2O yields the previously reported [CpFe(CO) 2]3Ga and gallium metal. Reaction of K[CpFe(CO)2] with GaI3 yields [CpFe(CO)2]GaI2, which upon hydrolysis gives the unusual galloxane, [CpFe(CO)2]6Ga 6(mu3-O)4(mu-OH)2I2. Reaction of K[CpFe(CO)2] with InCl in toluene results in the formation of previously reported [CpFe(CO)2]3In and indium metal. Reaction of CpMo(CO)3H with Ga(tBu)3 yields [CpMo(CO)3]Ga(tBu)2 which forms a Lewis acid-base complex with MeCN: [CpMo(CO)3]Ga(tBu) 2(MeCN). The structure of [CpMo(CO)3]Ga(tBu) 2 shows evidence of unusual intra- and inter-molecular carbonyl &cdots; gallium interactions.114 p.application/pdfengCopyright is held by the author, unless otherwise indicated. Permission to reuse, publish, or reproduce the work beyond the bounds of fair use or other exemptions to copyright law must be obtained from the copyright holder.Inorganic chemistryThesisTHESIS CHEM. 2001 BOROVIK