Inorganica ChimiaActa, 131 (1987) 27- 31 27 Octahedral Complexes of Ruthenium(I1) with some Fluorine Substituted Ditertiary Phosphines PRAMESH N. KAPOOR”, D. D. PATHAK, G. GAUR and P. C. MERCYKUTTY Department of Chemistry, University of Delhi, Delhi-l 10007, India (Received August 13, 1986) Abstract The ditertiary phosphines, 1-diphenylphosphino- 2-bis(m-fluorophenyl) phosphinoethane (la), l-di- phenylphosphino-2-bis(p-fluorophenyl) phosphino- ethane (lb), 1-diphenylphosphino-2-bis(m-trifluoro- methylphenyl) phosphinoethane (lc) complexes of ruthenium(I1) of the type [Ru(P-P’)sXs] (X = Cl, Br, I, NCS, P-P’= la, lb or lc) and [Ru(CO)s- (I-P’)Xa] (X = Cl, Br, I) have been prepared and characterized on the basis of elemental analysis, IR, UV ‘H NMR and 31P NMR (in a few cases) data. Based on the result of these studies, rrans- and cis- octahedral structures for [Ru(P-P’)2X2] and [Ru- (COh(?-P’)X*] complexes, respectively, have been proposed. In all these cases, the ditertiary phosphines act as potential bidentate chelating ligands. Introduction The tertiary phosphine complexes of ruthenium have occupied a unique position in the field of cata- lysis since the discovery of [RuHCl(PPh,),] which was reported to be an efficient and active hydrogena- tion catalyst zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA [l] . Tremendous efforts have been made to prepare a variety of monotertiary as well as ditertiary phosphine complexes of ruthenium in order to explore their catalytic behaviour [2-51. A survey of the literature reveals that although numerous complexes of ruthenium with sym- metrical ditertiary phosphines have been extensively studied [6-131, the chemistry of unsymmetrical ditertiary phosphines remained recessive [S] . Stu- dies of the unsymmetrical ditertiary phosphine com- plexes are much more informative in comparison to the symmetrical analogues since the 31P NMR spectra of the former can provide the direct measure- ment of phosphorus-phosphorus couplings, 2J *Author to whom correspondence should be addressed. 0020-1693/87/$3.50 (PMP). Further, the introduction of fluorine into the phenyl ring is expected to increase the solubi- lity characteristic of the resulting complexes, thereby, facilitating the 31P NMR studies. In this paper, we report the syntheses and characterization of eighteen complexes of three new fluorine substituted unsym- metrical ditertiary phosphines (la-lc) [16], there- by, substantially expanding our earlier studies [9]. la cl 0 P- O/ zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLK 0 CH2-CH2-- lo- o F ,P D OF lb (x 0 P-CH,-CH;, -P lc ‘CF, Experimental Physical measurements and experimental tech- niques were carried out as described elsewhere [9, 14-161. Ruthenium trichloride trihydrate was obtained from Johnson and Matthey Ltd., U.K. Dichlorotetrakis(dimethylsulphoxide)ruthenium(II), [RuCls(DMS0)4] [ 171 and dichlorodicarbonylruthe- nium(II), [Ru(CO),C12] 1181 were prepared by reported methods. 0 Elsevier Sequoia/Printed in Switzerland