The reaction of [RuHCl(CO)L] (L = PPh) with cyclohexylphosphine (PHCy) affords [RuHCl(CO)L(PHCy)], protonation of which in acetonitrile with HX affords [RuCl(NCMe)(CO)L(PHCy)]X (X = ClO, OTf, PF) salts while HCl provides [RuCl(CO)L(PHCy)]. The labile chloride and/or acetonitrile ligands are replaced by CO, CNCHMe-2,4,6, [EtNCS] or [Tp] (Tp = hydrotris(pyrazolyl)borate) to provide [RuCl(CO)L(PHCy)], [Ru[Cl(CO)(CNCHMe-2,4,6)L(PHCy)], [Ru(SCNEt)(CO)L(PHCy)] and [Ru(CO)L(Tp)(PHCy)] salts. Deprotonation of [RuCl(CO)L(PHCy)]OTf in benzene affords [RuCl(PHCy)(CO)L], but in methanol the secondary methoxyphosphine complex [Ru(CO)L{PH(OMe)Cy}] is obtained, as is [Ru(CO)(CNCHMe-2,4,6)L{PH(OMe)Cy}] from [Ru[Cl(CO)(CNCHMe-2,4,6)L(PHCy)]OTf. The reactions of [Ru(CO)L{PH(OMe)Cy}] with CO, CNCHMe-2,4,6 or dppe afford [Ru(CO)L{PH(OMe)Cy}], [Ru(CO)(CNCHMe-2,4,6)L{PH(OMe)Cy}] or [Ru(CO)(dppe){PH(OMe)Cy}], resectively, in each case demonstrating a preference for dissociation of PPh rather than PH(OMe)Cy. Aerial oxidation of [Ru(CO)L{PH(OMe)Cy}] results in oxidation of one carbonyl ligand with formation of the carbonato complex [Ru(OCO)(CO)L{PH(OMe)Cy}]. The reaction of [Ru(CO)L{PH(OMe)Cy}] with ethynyl benzene provides two diastereomers of [RuH(CCPh)(CO)L{PH(OMe)Cy}], while with anhydrous HCl, the cyclohexyl phosphine complex [RuCl(CO)L(PHCy)] is observed.

中文翻译：

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仲烷氧基膦的零价钌配合物

[RuHCl(CO)L] (L = PPh) 与环己基膦 (PHCy) 反应得到 [RuHCl(CO)L(PHCy)]，其在乙腈中用 HX 质子化得到 [RuCl(NCMe)(CO)L( PHCy)]X (X = ClO, OTf, PF) 盐，而 HCl 提供 [RuCl(CO)L(PHCy)]。不稳定的氯化物和/或乙腈配体被 CO、CNCHMe-2,4,6、[EtNCS] 或 [Tp] (Tp = 加氢三(吡唑基)硼酸盐) 取代以提供 [RuCl(CO)L(PHCy)]， [Ru[Cl(CO)(CNCHMe-2,4,6)L(PHCy)]、[Ru(SCNEt)(CO)L(PHCy)] 和 [Ru(CO)L(Tp)(PHCy)] 盐。 [RuCl(CO)L(PHCy)]OTf 在苯中去质子化得到 [RuCl(PHCy)(CO)L]，但在甲醇中得到仲甲氧基膦络合物 [Ru(CO)L{PH(OMe)Cy}] ，如[Ru[Cl(CO)(CNCHMe-2,4,6)L(PHCy)]OTf 中的[Ru(CO)(CNCHMe-2,4,6)L{PH(OMe)Cy}]。 [Ru(CO)L{PH(OMe)Cy}] 与 CO、CNCHMe-2,4,6 或 dppe 反应得到 [Ru(CO)L{PH(OMe)Cy}], [Ru(CO) (CNCHMe-2,4,6)L{PH(OMe)Cy}] 或 [Ru(CO)(dppe){PH(OMe)Cy}] 分别，在每种情况下都表明偏向于 PPh 解离而不是PH(OMe)Cy。 [Ru(CO)L{PH(OMe)Cy}] 的空气氧化导致一个羰基配体氧化，形成碳酸配合物 [Ru(OCO)(CO)L{PH(OMe)Cy}]。 [Ru(CO)L{PH(OMe)Cy}]与乙炔基苯反应生成[RuH(CCPh)(CO)L{PH(OMe)Cy}]的两种非对映异构体，而与无水HCl反应生成环己基膦观察到复合物 [RuCl(CO)L(PHCy)]。