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The half-sandwich 18- and 16-electron arene ruthenium iminophosphonamide complexes.
Peganova, Tat'yana A; Sinopalnikova, Iana S; Peregudov, Alexander S; Fedyanin, Ivan V; Demonceau, Albert; Ustynyuk, Nikolai A; Kalsin, Alexander M.
Afiliación
  • Peganova TA; A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov str., 119991 Moscow, Russia. kalsin@ineos.ac.ru.
Dalton Trans ; 45(42): 17030-17041, 2016 Nov 14.
Article en En | MEDLINE | ID: mdl-27711839
Novel half-sandwich 18e and 16e arene ruthenium iminophosphonamide complexes [(η6-C6Me6)RuCl{(R'N)2PR2}] (3a-c) and [(η6-C6Me6)Ru{(R'N)2PR2}]+(X-) (4a-c) (a, R = Ph, R' = p-Tol; b, R = Et, R' = p-Tol; c, R = Ph, R' = Me. X = BF4, PF6 or BArF4) were synthesized. The elongated Ru-Cl bond in the 18e complexes is shown to dissociate even in apolar solvents to form the corresponding 16e cations, which can be readily isolated as salts with non-coordinating anions. The coordinatively unsaturated 16e complexes are stable species due to efficient π-electron donation from the nitrogen atoms of the zwitterionic NPN-ligand. The ruthenium iminophosphonamides are moderately active in the ROMP polymerization of norbornene; the 16e complexes 4a,b yield high molecular weight polymers (Mn∼ 300 × 103) with a narrow distribution Mw/Mn∼ 1.6, while the 18e complexes 3a,b give polymers of lower molecular weight (Mn < 50 × 103) with a wider polydispersity index Mw/Mn∼ 2.5.
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Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Dalton Trans Asunto de la revista: QUIMICA Año: 2016 Tipo del documento: Article País de afiliación: Rusia Pais de publicación: Reino Unido
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Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Dalton Trans Asunto de la revista: QUIMICA Año: 2016 Tipo del documento: Article País de afiliación: Rusia Pais de publicación: Reino Unido