Grapperhaus Craig A, Venna Kiran B, Mashuta Mark S
Department of Chemistry, University of Louisville, Louisville, Kentucky 40292, USA.
Inorg Chem. 2007 Sep 17;46(19):8044-50. doi: 10.1021/ic701078e. 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.
在乙烯存在下，[Ru(DPPBT)₃]（1b，DPPBT = 2 - 二苯基膦苯硫醇盐）发生大量氧化反应，通过烯烃加成到顺式硫位点上生成六氟磷酸[(乙烷 - 1,2 - 二亚基双(硫代 - 2,1 - 亚苯基)二苯基膦)钌(II)]，[2a]PF₆。氧化过程中，1b在540、797和1041 nm处的吸收带强度降低。生成的配合物[2a]⁺在 +804 mV处显示出单一的氧化还原对。[2a]⁺的正电喷雾电离质谱（+ESI - MS）显示母离子峰在m/z = 1009.1013，³¹P核磁共振谱显示化学位移值δ(1) = 61.0，δ(2) = 40.3，δ(3) = 37.5，耦合常数J(12) ≈ J(13) ≈ 30 Hz且J(23) = 304 Hz。在 +1000 mV的保持电位下，[2a]⁺单电子氧化生成六氟磷酸[(乙烷 - 1,2 - 二亚基双(硫代 - 2,1 - 亚苯基)二苯基膦)钌(III)]，[2b][PF₆]₂。[2b][PF₆]₂的电子顺磁共振（EPR）显示出菱形信号，g(1) = 2.09，g(2) = 2.04，g(3) = 2.03。在包括1 - 己烯、苯乙烯、环己烯和降冰片烯在内的烯烃存在下，1b的氧化生成类似于[2a]⁺的产物。这些产物中的每一个都进一步氧化为[2b]²⁺的类似物。配合物[2a]⁺也可由[PPN][Ru(DPPBT)₃]（PPN [1a]；PPN = 双(三苯基膦亚基)铵）和1,2 - 二溴乙烷制备为溴化物盐。配合物[2a]Br以薄黄色片状晶体形式结晶，属于单斜空间群P2₁/c，晶胞参数为a = 10.2565(9) Å，b = 13.2338(12) Å，c = 38.325(3) Å，β = 93.3960(10)°。
