540772-29-0Relevant articles and documents
Isomeric preference in complexes of palladium(II) with chelating P,n-donor ligands
Del Campo, Olga,Carbayo, Arancha,Cuevas, Jose V.,Gabriel, Garcia-Herbosa,Munoz, Asuncion
experimental part, p. 2254 - 2260 (2009/12/02)
Square-planar complexes [PdCl{K2-(RN = CHC6H 4PPh2)Rj] (R = Cl; R = 4-CH 3C6H4, 1a; R = 2-CH3OC 6H4, 1b;R = 2- HOC6H4, 1c;R' =CH3; R = 4-CH3C6H4, 2a;R = 2-CH3OC6H4, 2b; R = 2-HOC6H 4, 2c) have been prepared and characterized. In complexes 2a-c only formation of one isomer was observed. The Pd-methyl bond arranges in a cis position to the phosphane fragment of the P,N chelating ligand. Reaction of complexes 2a-c in acetonitrile with AgBF4 led to removal of the chlorido ligand and coordination of acetonitrile for 2a. However, for 2b and 2c coordination of the oxygen was observed and the chelating P,N ligands became tricoord- inate. DFT calculations developed on models of the complexes displayed that the isomer with the methyl ligand coordinated in the cis position to the phosphane ligand were harder (or had a bigger HOMO/LUMO gap). Wiley-VCH Verlag GmbH & Co. KGaA.
Novel ruthenium(II) complexes containing imino- or aminophosphine ligands for catalytic transfer hydrogenation
Crochet, Pascale,Gimeno, Jose,Borge, Javier,Garcia-Granda, Santiago
, p. 414 - 420 (2007/10/03)
Five- and six-coordinate ruthenium(II) complexes containing imino- and aminophosphines have been prepared by ligand exchange processes. Thus, reactions of [RuCl2(PPh3)3] with 2-Ph2PC6H4CH=NR (R = Ph (1a); 2′,6′-C6H3Me2 (1b); 2′-C6H4OMe (1c)) lead to the chelate iminophosphine complexes [RuCl2(κ2-P,N-2-Ph2PC6H 4CH=NR)(PPh3)] (R = Ph (3a); 2′,6′-C6H3Me2 (3b)) and [RuCl2(κ3-P,N,O-2-Ph2PC6H 4CH=N-2′-C6H4OMe)(PPh3)] (3c), respectively. Similarly, reactions with aminophosphine ligands 2-Ph2PC6H4CH2NHR (R = Ph (2a); iPr (2d); (S)-CHMeCy (2e)) afford the 16-electron complexes [RuCl2(κ2-P,N-2-Ph2PC6H 4CH2NHR)(PPh3)] (R = Ph (5a); iPr (5d); (S)-CHMeCy (5e)). The iminophosphines 2-Ph2PC6H4CH=NR (R = iPr (1d); (S)-CHMeCy (1e)) react with [RuCl2(DMSO)4] to lead to the bis-iminophosphine complexes [RuCl2(κ2-P,N-2-Ph2PC6H 4CH=NR)2] (R = iPr (4d); (S)-CHMeCy (4e)). The crystal structure of 4d has been determined by X-ray diffraction. Complexes 3a-c, 4d,e and 5a,d,e are active in catalytic transfer hydrogenation of acetophenone. All of them are more efficient than the precursor [RuCl2(PPh3)3].