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American Chemical Society, Inorganic Chemistry, 10(42), p. 3293-3307, 2003

DOI: 10.1021/ic020702k

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Ruthenium(II) and Ruthenium(IV) Complexes Containing κ1-P-, κ2-P,O-, and κ3-P,N,O-Iminophosphorane-Phosphine Ligands Ph2PCH2P{NP(O)(OR)2}Ph2(R = Et, Ph):  Synthesis, Reactivity, Theoretical Studies, and Catalytic Activity in Transfer Hydrogenation of Cyclohexanone

Journal article published in 2003 by Victorio Cadierno, Pascale Crochet, Josefina Díez, Joaquín García-Álvarez, Sergio E. García-Garrido, José Gimeno, Santiago García-Granda, Miguel A. Rodríguez ORCID
This paper is available in a repository.
This paper is available in a repository.

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Abstract

[(Ru(η6-p-cymene)(m-Cl)Cl)2] and [(Ru(η3:η3-C10H16)(mu-Cl)Cl)2] react with Ph2PCH2P[=NP(=O)(OR)2]Ph2 (R = Et (1a), Ph (1b)) affording complexes [Ru(η6-p-cymene)Cl2(kappa(1)-P-Ph2PCH2P[=NP(=O)(OR)2]Ph(2))] (R = Et (2a), Ph (2b)) and [Ru(η3:η3-C10H16)Cl2(kappa(1)-P-Ph2PCH2P[=NP(=O)(OR)2]Ph2)] (R = Et (6a), Ph (6b)). While treatment of 2a with 1 equiv of AgSbF6 yields a mixture of [Ru(η6-p-cymene)Cl(kappa(2)-P,O-Ph2PCH2P[=NP(=O)(OEt)2]Ph2)][SbF6] (3a) and [Ru(η6-p-cymene)Cl(kappa(2)-P,N-Ph2PCH2P[=NP(=O)(OEt)2]Ph2)][SbF6] (4a), [Ru(η6-p-cymene)Cl(kappa(2)-P,O-Ph2PCH2P[=NP(=O)(OPh)2]Ph2)][SbF6] (3b) and [Ru(η3:η3-C10H16)Cl(kappa(2)-P,O-Ph2PCH2P[=NP(=O)(OR)2]Ph2)][SbF6] (R = Et (7a), Ph (7b)) are selectively formed from 2b and 6a,b. Complexes [Ru(η6-p-cymene)(kappa(3)-P,N,O-Ph2PCH2P[=NP(=O)(OR)2]Ph2)][SbF6]2 (R = Et (5a), Ph (5b)) and [Ru(η3:η3-C10H16)(kappa(3)-P,N,O-Ph2PCH2P[=NP(=O)(OR)2]Ph2)][SbF6]2 (R = Et (8a), Ph (8b)) have been prepared using 2 equiv of AgSbF6. The reactivity of 3-5a,b has been explored allowing the synthesis of [Ru(η6-p-cymene)X2(kappa(1)-P-Ph(2)PCH2P[=NP(=O)(OR)2]Ph2)] (R = Et, Ph; X = Br, I, N3, NCO (9-12a,b)). The catalytic activity of 2-8a,b in transfer hydrogenation of cyclohexanone, as well as theoretical calculations on the models [Ru(η6-C6H6)Cl(kappa(2)-P,N-H(2)PCH2P[=NP(=O)(OH)2]H2)]+ and [Ru(η6-C6H6)Cl(kappa(2)-P,O-H(2)PCH2P[=NP(=O)(OH)2]H2)]+, has been also studied.