Discovery of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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Synthetic Route of 32993-05-8, An article , which mentions 32993-05-8, molecular formula is C41H35ClP2Ru. The compound – Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II) played an important role in people’s production and life.

Metal complexes of a series of diphosphorus ligands, 4-(difluorophosphino)-2,5-dimethyl-2H-1,2,3sigma2-diazaphosphole (1), 4-(bis(dimethylaminophosphino)-2,5-dimethyl-2H-1,2,3sigma 2-diazaphosphole (2), and 4-bis(1,1,1-trifluoroethoxyphosphino)-2,5-dimethyl-2H-1,2,3sigma 2-diazaphosphole (3), were prepared. Ligand 1 reacted with CpRu(PPh3)2Cl to give the diastereotopic complex CpRu(PPh3)(1)Cl (4). With CpRh(CO)2 this same ligand gave CpRh(1)2 (5), which was structurally characterized. The Cp-rhodium center carries two difluorophosphinodiazaphole ligands. The P-N bond distances, (1.670(4) and 1.672(3) A), suggest partial multiple-bond character. [Cp*Rh(Cl)2] with (1) gave Cp*Rh(Cl)2(1). Ligand 2 with [Rh(CO)2Cl]2 gave trans-Rh(CO)Cl(2)2 (7), which was structurally characterized. The structure reveals two square-planar isomers in 75:25 ratio differing only in the interchange of Cl and CO. The two diazaphosphole ligands lie trans to each other and the planar diazaphosphole rings are oriented perpendicular to the square plane, stacked so that a mirror plane exists through the Cl-Rh-CO plane. The phosphorus-rhodium distance is 2.33 A. The average P-N bond distance of the exo-phosphorus center and the dimethylamino groups is 1.683 A, shorter than the normally accepted single-bond length. The dimethylamino nitrogen atoms on the exo-phosphorus are planar. Similarly, ligand 3 with [Rh(CO)2Cl]2 gave trans-[Rh(CO)Cl(3)2] (8). The ligand action ranges in reactivity from a similarity to phenylphosphines through to PF3, reflecting the variation in basicity induced by substituent changes on the exo-phosphorus.

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Reference：
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI