Department of Chemistry, University of Louisville, 2320 South Brook Street, Louisville, Kentucky 40292, USA.
Inorg Chem. 2012 Jul 16;51(14):7913-20. doi: 10.1021/ic300983x. Epub 2012 Jun 29.
Chemical oxidation of tris(2-diphenylphosphinebenzenethiolato)ruthenate(II) Ru-1 with ferrocenium hexafluorophosphate in the presence of ethylene yields [(2-diphenylphosphinebenzenethiolato)(ethane-1,2-diylbis(thio-2,1-phenylene)diphenylphosphine)ruthenium(II)] hexafluorophosphate, [Ru-1·C(2)H(4)]PF(6), from addition of the alkene across cis sulfur sites. The Ru-1·C(2)H(4) complex displays a single redox couple at +794 mV versus ferrocenium/ferrocene. (1)H NMR of Ru-1·C(2)H(4) displays ethylene resonances at δ = 1.29 (td, 1H), 1.59 (td, 1H), 2.78 (dd, 1H), and 3.03 (dd, 1H). In the presence of base Ru-1·C(2)H(4) is selectively deprotonated at the pseudoequatorial proton on the carbon α to the sulfur trans to phosphorus, yielding the vinyl metallosulfonium derivative [Ru-1·C(2)H(3)]. (1)H and (31)P NMR spectra of [Ru-1·C(2)H(3)] are temperature dependent, associated with inversion of the sulfur lone pair at the vinyl metallosulfonium. The activation energy for the fluxional process calculated using density functional theory (B3LYP/LANL2DZ+6-31g) of 14.36 kcal/mol is consistent with the experimentally determined value of 13.08 kcal/mol. The complex [Ru-1·C(2)H(3)] crystallizes as yellow blocks in the triclinic space group P-1 with unit cell dimensions of a = 11.2718(5) Å, b =12.0524(3) Å, c = 23.6075(10) Å, α = 101.715(3)°, β = 98.154(4)°, and γ = 105.209(3)°. Addition of hydrochloric acid to [Ru-1·C(2)H(3)] regenerates Ru-1·C(2)H(4). Addition of DCl confirms the selectivity of this reverse reaction.
三（2-二苯基膦苯硫醇）钌（II）Ru-1与六氟磷酸铁在乙烯存在下的化学氧化生成[(2-二苯基膦苯硫醇)(乙烷-1,2-二基双（硫-2,1-亚苯基）二苯基膦)钌（II)]六氟磷酸盐，[Ru-1·C（2）H（4）]PF（6），这是由于烯烃在顺式硫原子上的加成。Ru-1·C（2）H（4）络合物在相对于 ferrocenium/ferrocene 的 +794 mV 处显示出一个单一的氧化还原偶对。Ru-1·C（2）H（4）的（1）H NMR 显示乙烯的共振在 δ = 1.29（td，1H），1.59（td，1H），2.78（dd，1H）和 3.03（dd，1H）。在碱的存在下，Ru-1·C（2）H（4）选择性地在磷 trans 位上的硫 trans 位上的碳α上的假轴向质子上脱质子，生成乙烯基金属硫翁衍生物[Ru-1·C（2）H（3）]。[Ru-1·C（2）H（3）]的（1）H 和（31）P NMR 光谱随温度变化，这与乙烯基金属硫翁中的硫孤对的反转有关。使用密度泛函理论（B3LYP/LANL2DZ+6-31g）计算得到的通量态过程的活化能为 14.36 kcal/mol，与实验测定的值 13.08 kcal/mol 一致。配合物[Ru-1·C（2）H（3）]结晶为黄色块状物，属于三斜晶系 P-1 空间群，其晶胞参数为 a = 11.2718(5) Å，b =12.0524(3) Å，c = 23.6075(10) Å，α = 101.715(3)°，β = 98.154(4)°，γ = 105.209(3)°。盐酸的加入使[Ru-1·C（2）H（3）]再生Ru-1·C（2）H（4）。DCl 的加入证实了该逆反应的选择性。
