Three new carboxylic acid functionalised diphosphines, R₂PCH₂N(Ar)CH₂PR₂ [^CyL₁ R = Cy, Ar = (1-CO₂H)(3-OMe)C₆H₃, ^CyL₂ R = Cy, Ar = (1-CO₂H)(3-OH)C₆H₃ and ^PhL₃ R = Ph, Ar = (1-CO₂H)(5-OMe)C₆H₃] have been prepared from condensation of R₂PCH₂OH and the appropriate aromatic amine in MeOH, and isolated as colourless solids (for ^CyL₁, ^CyL₂) in good yield. Reaction of ^CyL₁, ^CyL₂, or ^PhL₃, along with the previously reported diphosphines ^PhL₁, ^PhL₂, and ^PhL₄, and [RuCl(μ-Cl)(η⁶-Me₂CHC₆H₄Me)]₂ in CH₂Cl₂ affords the P/P-bridging dinuclear ruthenium(II) complexes {RuCl₂(η⁶-Me₂CHC₆H₄Me)}₂(μ-^CyL₁−^PhL₄) 1a−f as red/orange solids. Careful monitoring by ³¹P{¹H} NMR spectroscopy of CDCl₃ solutions of 1a−e revealed remarkably clean P−C_sp3 bond cleavage to give Ru^II mononuclear species 2a−e and the known secondary phosphine complexes RuCl₂(η⁶-Me₂CHC₆H₄Me)(PCy₂H) 3 and RuCl₂(η⁶-Me₂CHC₆H₄Me)(PPh₂H) 4. Furthermore, facile P−C_sp³ bond cleavage of ^PhL₁ can be observed using the chloro-bridged dimers [IrCl(μ-Cl)(η⁵-C₅Me₅)]₂ or [RhCl(μ-Cl)(η⁵-C₅Me₅)]₂ instead. Deuterium labelling of ^CyL₁, ^CyL₁, ^PhL₁, and ^PhL₂ enabled the assignment of the methylene protons to be confirmed from ¹H NMR spectroscopy. All new compounds have been characterised using a range of spectroscopic and analytical techniques. Single crystal X-ray structures have been determined for ^CyL₁, 1d·3OEt_2, 1f·2CDCl₃·OEt₂, 2b, 2c, 2d·CDCl₃, 2e·0.5OEt₂ and 6b·1.5CDCl₃. The free phenolic group in ^CyL₁, 1d·3OEt_2, 1f·2CDCl₃·OEt₂, 2b and 2d·CDCl₃ participates in intra- or intermolecular O−H···O hydrogen bonding.

三种新的羧酸官能化的二膦R ₂ PCH ₂ N（Ar）CH ₂ PR ₂ [ ^Cy L ₁ R = Cy，Ar =（1-CO ₂ H）（3-OMe）C ₆ H ₃，^Cy L ₂ R ＝ Cy，Ar ＝（1-CO ₂ H）（3-OH）C ₆ H ₃，^Ph L ₃ R ＝ Ph，Ar ＝（1-CO ₂ H）（5-OMe）C ₆ H ₃ ]由R ₂ PCH ₂缩合制备OH和适当的芳族胺在MeOH中的溶液，并以良好收率分离为无色固体（对于^Cy L ₁，^Cy L ₂）。的反应^赛扬大号₁，^赛扬大号₂，或^博士大号₃，沿与先前报道的二膦^博士大号₁，^博士大号₂，和^博士大号₄，和将[RuCl（μ-Cl）的（η ⁶ -Me ₂ CHC ₆ H ₄ Me）] ₂ in CH ₂ Cl ₂，得到P / P-桥接的双核钌（II）络合物的RuCl { ₂（η ⁶ -Me ₂ CHC ₆ H ^ ₄ Me）的} ₂（μ-^赛扬大号₁ -^博士大号₄）1A - ˚F为红色/橙色固体。用³¹ P { ¹ H} NMR光谱对1a - e的CDCl ₃溶液进行仔细监测，发现明显清洁的Pc _SP3键裂解，得到Ru ^II单核物种2a - e和已知的仲膦络合物的RuCl ₂（η ⁶ -Me ₂ CHC ₆ H ^ ₄ ME）（PCY ₂ 2H）3和的RuCl ₂（η ⁶ -Me ₂ CHC ₆ H ^ ₄ ME）（PPH ₂ 2H）4。此外，容易对-C _SP ³的键裂解^博士大号₁可以使用氯桥二聚体[的IrCl（μ-Cl）的（η可以观察到⁵ -C ₅我₅）] ₂或[的RhCl（μ-Cl）的（ η ⁵ -C₅ Me ₅）] ₂代替。^Cy L ₁，  ^Cy L ₁，  ^Ph L ₁和^Ph L _2的氘标记 使得能够通过¹ H NMR光谱确认亚甲基质子的分配。所有新化合物已使用多种光谱和分析技术进行了表征。已被确定为单晶X射线结构^赛扬大号₁，1D ·3OEt _2， 1F ·2CDCl ₃ ·OET ₂，2B，2C，2D ·CDCL₃，2E ·0.5OEt ₂和图6b ·1.5CDCl ₃。游离酚基在^赛扬大号₁，1D ·3OEt _2， 1F ·2CDCl ₃ ·OET ₂，图2b和2d中·CDCL _3个参与了分子内或分子间的O - H···O氢键键合。