9/22 News Extracurricular laboratory:new discovery of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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Electric Literature of 32993-05-8. Chemistry is an experimental science, and the best way to enjoy it and learn about it is performing experiments.Introducing a new discovery about 32993-05-8, Name is Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

Reactions of ethyne with [Ru3(mu-dppm)(CO)10] have given isomeric complexes [Ru3(mu3-C6H6)(CO) 6(dppm)], one of which, 2, contains the dppm chelating an Ru-atom, together with a hexatrienetriyl ligand attached to the Ru3 cluster to form a methylideneruthenacyclohexadiene system. The second isomer 3 contains the dppm bridging an Ru-Ru bond, with the C6H6 ligand forming a vinylruthenacyclopentadiene system. Also isolated was the open-chain Ru3 complex 4 containing a ruthenacyclopentadiene attached to the central Ru-atom; the other Ru-Ru vector is bridged by a PPh2CHPPh2C4H5 ligand, formed by a novel insertion of two ethyne molecules into an Ru-P bond. The reaction of ethyne with [Ru3(mu-H)(mu3-C2H 2)(CO)9] proceeded by attack at the coordinated alkyne and at the cluster to give a cluster-bonded PPh2CH2PPh2CCH system in 7. Thermolysis of [Ru3(mu-H)(mu3-C2SiMe3) (mu-dppm)(CO)7] (8; refluxing MeOH) in the presence of KF gave [Ru6(mu-CCH2)2(mu-dppm)2(CO) 12] (9; 80%); similar reactions carried out with [RuClCp(PPh3)2] also present gave 9 (67%) together with [Ru3(mu-H)(mu3-C2H)(mu-dppm)(CO) 6(PPh3)] (11; 23%). The molecular structures of 2, 3, 4, 7, 9, and 11, some as differently solvated forms, have been determined by single-crystal X-ray studies.

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