| 17705371 |
Grapperhaus CA, Venna KB, Mashuta MS: Carbon-sulfur bond formation via alkene addition to an oxidized ruthenium thiolate. Inorg Chem. 2007 Sep 17;46(19):8044-50. Epub 2007 Aug 17.
Bulk oxidation of [Ru (DPPBT) 3], 1b, (DPPBT = 2-diphenylphosphinobenzenethiolate) in the presence of ethylene yields [(ethane-1,2-diylbis (thio-2,1-phenylene) diphenylphosphine) ruthenium (II)] hexafluorophosphate, [2a] PF6, from the addition of the alkene across cis sulfur sites. During oxidation, the absorption bands of 1b at 540, 797, and 1041 nm decrease in intensity. The resulting complex [2a]+ displays a single redox couple at +804 mV. The +ESI-MS of [2a]+ shows a parent ion peak at m/z = 1009.1013, and the 31P NMR spectrum displays chemical shift values of delta (1) = 61.0, delta (2) = 40.3, and delta (3) = 37.5 with coupling constants of J (12) approximately J (13) approximately 30 Hz and J (23) = 304 Hz. Oxidation of [2a]+ by one electron at a holding potential of +1000 mV yields [(ethane-1,2-diylbis (thio-2,1-phenylene) diphenyl phosphine) ruthenium (III)] hexafluorophosphate, [2b][PF6] 2. The EPR of [2b][PF6] 2 displays a rhombic signal with g (1) = 2.09, g (2) = 2.04, and g (3) = 2.03. Oxidation of 1b in the presence of alkenes including 1-hexene, styrene, cyclohexene, and norbornene yields products similar to [2a]+. Each of these products was further oxidized to an analogue of [2b] 2+. Complex [2a]+ was also prepared, as the bromide salt, from [PPN][Ru (DPPBT) 3] (PPN [1a]; PPN = bis (triphenylphosphoranylidene) ammonium) and 1,2-dibromoethane. The complex [2a] Br crystallizes as thin yellow plates in the monoclinic space group P21/c with unit cell dimensions of a = 10.2565 (9) A, b = 13.2338 (12) A, c = 38.325 (3) A, and beta = 93.3960 (10) degrees. |
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