Discovery of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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Electric Literature of 246047-72-3. Let’s face it, organic chemistry can seem difficult to learn. Especially from a beginner’s point of view. Like 246047-72-3, Name is (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium. In a document type is Article, introducing its new discovery.

A series of Ru-based olefin metathesis catalysts containing N,N?-diamidocarbenes (DACs) were synthesized and studied. X-ray crystallographic analysis revealed that the Ru-Ccarbene distances (1.938(5)-1.984(4) A) measured in the DAC-supported complexes were relatively short, particularly in comparison to the range of Ru-C carbene distances typically observed in analogous N-heterocyclic carbene (NHC) supported complexes (1.96-2.03 A). While the Tolman electronic parameters (TEP) of various DACs (2056-2057 cm-1) were calculated to be similar to that of PCy3 (2056 cm-1), the ring-closing metathesis (RCM) of diethyl diallylmalonate facilitated by DAC-supported Ru complexes proceeded at a relatively slow rate. However, unlike the phosphine-containing complexes, the DAC analogues catalyzed the RCM of diethyl dimethallylmalonate to its respective tetrasubstituted olefin. A series of electrochemical experiments revealed that the Ru complexes bearing a DAC ligand underwent oxidation at significantly higher potentials (DeltaE pa > 0.5 V) than analogous complexes containing phosphines and various N-heterocyclic carbenes (NHCs), including a tetrahydropyrimidinylidene, a saturated and strongly donating NHC analogue of the DAC. The relative catalytic activities observed were attributed to the steric properties of the aforementioned ligands.

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