UBC Theses and Dissertations
The syntheses and reactions of carbonyl(phosphine)(thiolator)ruthenium(II) complexes Jessop, Philip Gregory
The chemistry of homogeneous transition metal systems offer parallels to the reactions on the surfaces of industrial hydrodesulphurization catalysts. The reactions of several ruthenium complexes with sulphur-containing reagents are described, with an emphasis on the kinetics and mechanisms thereof. The complex Ru(CO)₂(PPh₃)₃ (2), for example, reacts quickly with thiols and disulphides, producing cct-RuH(SR)(CO)₂(PPh₃)₂ (9) and cct-Ru(SR)₂(CO)₂(PPh₃)₂ (14), respectively, although 2 fails to react with unstrained thioethers. Reactions of the related complex Ru(CO)₂(PPh₃)(dpm) (dpm=Ph₂PCH₂PPh₂) are complicated by the lability of all of the three different ligands. The two dihydrides cct-RuH₂(CO)₂(PPh₃)₂ (3) and RuH₂(dpm)₂, as a cis/trans mixture (7), react with thiols to produce the hydrido-thiolato complexes 9 and RuH(SR)(dpm)₂ (13). respectively. The mechanisms appear to depend on the basicity of the hydride ligands; the more basic dihydride, 7, is probably protonated by the thiol, giving an unobserved molecular hydrogen intermediate, while 3 reacts by slow reductive elimination of H₂. The same rate constant, rate law, and activation parameters are found for the reaction of 3 with thiols, CO or PPh₃. The reaction of 3 with RSSR produces mostly 9, with small amounts of 14. The complete characterization of several members of the series 9 and 14 is described, including the crystal structure of the p-thiocresolate example of each. The reactions of 9 with other thiols, P(C₆H₄pCH₃)₃, CO, RSSR, HCl, PPh₃, and H₂, are also reported. The first three of these reactions share the same rate law and rate constant, the common rate determining step probably being initial loss of PPh₃. Some equilibrium constants for the exchange reactions of 9d (R=CH₂CH₃) with other thiols were tetermined, the Keq values increasing with the acidity of the incoming thiol. The mercapto hydrogens of 9a and 14a (R=H) exchange with the acidic deuterons of added CD₃OD. The hydridic and ortho-phenyl hydrogens exchange more slowly, presumably by intramolecular processes. Complex 14b (R=C₆H₄pCH₃) is unstable in the presence of light, exchanges phosphines rapidly with added P(C₆H₄pCH₃)₃, exchanges thiolate groups with added thiols, and is converted by high pressures of H₂ to a mixture of 9b and 3. Intermediates proposed for the mechanism of the thiol exchange reactions of 9 and 14 contain two or three thiolate groups sharing a proton. A related complex, [Ru(CO)₂(PPh₃)(μSEt)₂(μ₃SEt)Na(THF)]₂, which contains three thiolate groups on a ruthenium centre sharing a sodium cation, was isolated from the reaction of cct-RuCl₂(CO)₂(PPh₃)₂ with sodium ethanethiolate. In acetone, 9b and 14b can be formed cleanly from cct-RuHCl(CO)₂(PPh₃)₂ and cct-RuCl₂(CO)₂(PPh₃)₂, respectively, by reaction with p-thiocresolate. Complex 3 or cheaper analogues could be used as catalysts for the reduction of disulphides by H₂, or as recyclable reagents for the non-oxidative extraction of thiols from thiol-containing mixtures such as oil fractions. The chemistry described above will help to guide future researchers to systems that more closely parallel the processes occurring on the surfaces of industrial hydrodesulphurization catalysts.
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