Ruthenium(II), copper(I) and silver(I) complexes of large bite bisphosphinite, bis(2-diphenylphosphinoxynaphthalen-1-yl)methane: Application of Ru(II) complexes towards the hydrogenation of styrene and phenylacetylene
作者:Benudhar Punji、Joel T. Mague、Maravanji S. Balakrishna
DOI:10.1016/j.jorganchem.2006.06.040
日期:2006.10
Ruthenium(II), copper(I) and silver(I) complexes of large bite bisphosphinite Ph2P((-OC10H6)(mu-CH2)(C10H6O-)}PPh2 (1) are described. Reactions of bisphosphinite 1 with [Ru(eta(6)-p-cymene)(mu-Cl)Cl](2) and RuCl2(PPh3)(3) afford mono- and bis-chelate complexes [RuCl(eta(6)-p-cymene)eta(2)-Ph2P(-OC10H6)(mu-CH2)(C10H6O-)}PPh2-kP,kP}]Cl (2) and trans-[RuCl2eta(2)-Ph2P(-OC10H6)(mu-CH2)(C10H6O-)}PPh2-KP,KP)(2)] (3), respectively. Treatment of 1 with CuX (X = Cl, Br and I) furnish 10-membered chelate complexes of the type [Cu(X)eta(2)-Ph2P(-OC10H6)(mu-CH2)(C10H6O-)PPh2-kP, kP}] (4, X = Cl; 5, X = Br; 6, X = I), whereas [Cu(MeCN)(4)]PF6 affords a bis-chelated cationic complex [Cueta(2)-Ph2P(-OC10H6)(mu-CH2)(C10H6O-)PPh2-kP,kP)(2)][PF6] (7). Reaction between 1 and AgOTf produce both mono- and bis-chelated complexes [Ageta(2)-Ph2P(-OC10H6)(mu-CH2)(C10H6O-)PPh2-kP,kP)(SO3CF3)] (8) and [Ageta(2)- Ph2P(-OC10H6)(mu-CH2)(C10H6O-)PPh2-kP,kP}(2)][SO3CF3](9), respectively; whereas the similar reaction of 1 with[Ag(OTf)PPh3] affords chelate complex of the type [Ageta(2)-Ph2P(-OC10H6)(mu-CH2)(C10H6O-)PPh2-kP,kP}(PPh3)(SO3CF3)] (10). All the complexes were characterized by H-1 NMR, P-31 NMR, elemental analysis and mass spectrometry, including low-temperature NMR studies in the case of silver complexes. The molecular structures of 4 and 6 are determined by X-ray diffraction studies. Ruthenium complexes 2 and 3 promote catalytic hydrogenation of styrene and phenylacetylene with good turnover numbers. (c) 2006 Elsevier B.V. All rights reserved.