A simple procedure for the preparation of [(S)Ru(η-C5H5)(S)dpompyr-PP′H] [dpompyr = N-diphenylphosphino-2-(diphenylphosphinoxymethyl)pyrrolidine] from [Ru3(CO)12] is described. The hydride reacts stereospecifically with chloroform or carbon tetrachloride to give [(S)Ru(η-C5H5)(S)dpompyr-PP′Cl] whose structure is reported. The crystals are monoclinic, space group P21 with a = 11.076(2), b = 10.908(2), c = 12.825(3) Å, β = 92.26(2), and Z = 2. The structure was solved by the heavy-atom method and refined to R = 0.0322 using 2 306 diffractometer data with I > 3σ(I). Synthesis of this chloro-complex from [Ru(η-C5H5)(PPh3)2Cl] and (S)dpompyr proceeds with only modest diastereoselectivity whereas reduction of [(S)Ru(η-C5H5)(S)dpompyr-PP′Cl] using LiAlH4 regenerates 88% [(S)Ru(η-C5H5)(S)dpompyr-PP′H]. Mechanisms are proposed to explain the observed diastereoselectivities. Circular dichroism and 1H, 13C, and 31P n.m.r. spectra of all new compounds are also reported.
Synthesis and stereochemical studies of the chiral ruthenium complexes [Ru(η-C5H5)(S)dpompyr-PP′X] [dpompyr = N-diphenylphosphino-2-(diphenylphosphinoxymethyl)pyrrolidine, X = H or Cl]. Crystal structure of [(S)Ru(η-C5H5)(S)dpompyr-PP′Cl] / E. Cesarotti, L. Prati, A. Sironi, G. Ciani, C. White. - In: JOURNAL OF THE CHEMICAL SOCIETY DALTON TRANSACTIONS. - ISSN 0300-9246. - :5(1987), pp. 1149-1155.
Synthesis and stereochemical studies of the chiral ruthenium complexes [Ru(η-C5H5)(S)dpompyr-PP′X] [dpompyr = N-diphenylphosphino-2-(diphenylphosphinoxymethyl)pyrrolidine, X = H or Cl]. Crystal structure of [(S)Ru(η-C5H5)(S)dpompyr-PP′Cl]
E. CesarottiPrimo
;L. PratiSecondo
;A. Sironi;G. CianiPenultimo
;
1987
Abstract
A simple procedure for the preparation of [(S)Ru(η-C5H5)(S)dpompyr-PP′H] [dpompyr = N-diphenylphosphino-2-(diphenylphosphinoxymethyl)pyrrolidine] from [Ru3(CO)12] is described. The hydride reacts stereospecifically with chloroform or carbon tetrachloride to give [(S)Ru(η-C5H5)(S)dpompyr-PP′Cl] whose structure is reported. The crystals are monoclinic, space group P21 with a = 11.076(2), b = 10.908(2), c = 12.825(3) Å, β = 92.26(2), and Z = 2. The structure was solved by the heavy-atom method and refined to R = 0.0322 using 2 306 diffractometer data with I > 3σ(I). Synthesis of this chloro-complex from [Ru(η-C5H5)(PPh3)2Cl] and (S)dpompyr proceeds with only modest diastereoselectivity whereas reduction of [(S)Ru(η-C5H5)(S)dpompyr-PP′Cl] using LiAlH4 regenerates 88% [(S)Ru(η-C5H5)(S)dpompyr-PP′H]. Mechanisms are proposed to explain the observed diastereoselectivities. Circular dichroism and 1H, 13C, and 31P n.m.r. spectra of all new compounds are also reported.Pubblicazioni consigliate
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