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. Cesarotti
Primo
;
L. Prati
Secondo
;
A. Sironi;G. Ciani
Penultimo
;
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.
Settore CHIM/03 - Chimica Generale e Inorganica
Article (author)
File in questo prodotto:
Non ci sono file associati a questo prodotto.
Pubblicazioni consigliate

Caricamento pubblicazioni consigliate

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/187992
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 19
  • ???jsp.display-item.citation.isi??? ND
social impact