Research Journal of Chemical Sciences ______________________________________________ ISSN 2231-606X Vol. 3(6), 81-82, June (2013) Res. J. Chem. Sci. International Science Congress Association 81 Short Communication Triphenylphosphine Sulphide as a Complexing Agent : Synthesis and Characterisation of Complexes of Rhodium (I) and Ruthenium (II)Yadav S.N., Kumar Vijay, Singh R.N. and Shubhra Prabha*P.G. Centre, Department of Chemistry, College of Commerce, Patna-8000 020, INDIAAvailable online at: www.isca.in Received 7th February 2013, revised 27th March 2013, accepted 25th April 2013Abstract Rhodium(I) complexes of Wilkinson's catalyst [Rh(P.Ph)Cl] types, have been synthesised and characterised by elemental analysis, IR, H NMR, 13C NMR and magnetic measurements. The complexes have been found to be four coordinated with square planar geometry around the Rhodium metal ions with diamagnetic character, while ruthenium metal forms five coordinated with trigonal bipyramid geometry with paramagnetic character. Keywords: Triphenylphosphine Sulphide, Rhodium (I), Ruthenium (II), Wilkinson's catalyst, complexes. IntroductionWilkinson's catalyst [Rh(P.PhCl]1–4 was first synthesised by Wilkinson in 1965 by heating rhodium chloride RhCl.3HO with triphenyl phosphine in boiling ethanol. It is a square planar complex having three bulky triphenylphosphine ligands. Rhodium(I) complexes of the types [Rh(CO)LL(P.Ph] have been synthesised and characterised by K. Natrajan et. al. and proposed the structure on the basis of elemental analysis, IR, 31P NMR and electronic measurements. Hydridophosphine complexes of rhodium and ruthenium have been synthesised and characterised Rh. H[(CP], and [H Rh(CP] by Kenneth et al; some typical phosphine complexes of ruthenium such as [RuClH(P.Ph], [RuH(P.Ph] [Ru(CO)(P.Ph] [Ru(acac) (P.Ph] [Ru(C) (P.Me] [Ru H(PMe etc. have been already known. A number of metal complexes of Ru(II) and Rh(I) with mixed ligand complexes of composition [Ru(CO)(LL)(P.PhCl] and [Ru H(CO)(LL)(P.Ph] [Rh(CO)(LL)(P.Ph] and [Rh(LL) (P.Ph] have been synthesised and characterized by elemental analysis, IR and electronic spectral measurements by K. Natrajan et. al. where LL = -diketonate/monothio--diketonate. Ruthenium complexes of sulphur containing ligands such as [Ru(SH)(CO)(P.Ph9 [Ru(SCNEt(P.Ph10 have been also synthesised and characterized by various chemists11-12. In this paper, we have described the synthesis of mononuclear rhodium(I) and ruthenium(II) complexes with triphenylphosphine sulphide ligand in the field of organometallic compounds. The complexes thus prepared have been characterised and structures proposed on the basis of spectral (IR, NMR), magnetic measurements and analytical data. Material and Methods The analysis of ligand and its metal complexes with physical measurements (IR, NMR etc.) have been performed from SAIF, IIT, Powai, Mumbai. The ligand TPPS(L) was prepared by reported methods13-14Preparation of [Rh L Cl] complex: 100mg Wilkinson's catalyst was treated with 10ml methanol and benzene mixture 250mg ligand was dissolved in 20ml benzene and were mixed in above solution. The mixture become reddish brown. It was distilled for 3-hours to give required product [RhLCl]. It was washed with ethanol and dried in vacuo. Preparation of [RuLCl] Complex: An aqueous alcoholic solution of ruthenium(III) chloride was treated with alcoholic benzene mixture of ligand in 1 : 3 molar ratio. The reaction was distilled for 3-hours to give red required product. The resulting solid was washed with ethanol and dried in vacuo. Results and DiscussionThe complexes of Rh and Ru II with triphenylphosphine sulphide (TPPS) ligand were prepared. The colour of these complexes are reddish brown/ red coloured. They are stable in air and are nonhygroscopic. They are slightly soluble in ethanol fairly soluble in DMF as well as in benzene. They are insoluble is water. The compositions of the complexes have been represented as RhLCl and RuLCl. The rhodium(I) complex is found to be diamagnetic while ruthenium(II) is found to be paramagnetic. Infrared spectra : The ir-stretching strong bands have been found between 3057-3054 cm–1 attributed to (C–H) vibrations and the band is not effected appreciably by substituent groups15. Bands near 1963, 1906, 1827 and 1775 cm–1 are due to substituted benzene ring, as substituted benzene also show speaks in 2000-1670 cm–1 region16. The IR-spectrum of ligand and its metal complexes display medium and weak bands in region 1672-1624 cm–1 and 1590-1583 cm–1 attributed to carbon-carbon multiple bond stretching vibrations. The ligand and complexes also exhibit a very strong absorption band in the range of 1480-1435 cm–1 attributed to phenyl ring skeletal vibrations due to (C = C) and (C–C) vibrations. Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 3(6), 81-82, June (2013) Res. J. Chem. Sci. International Science Congress Association 82 Table-1 Characteristic IR frequencies (cm–1) of ligand and complexesComp. uu(C–H) Phenyl ring Phenyl ring skeletal vibration dd(C–H) and (C–C) vibration uu(P–C) stretch uu(P=S) Aromatic ring singly substituted u (C=C) u (C–C) TPPS 3057 1668 1585 1480 1435 1274 1182 929 754 692 638 [RhL 3 Cl] 3056 1624 1590 1484 1438 1267 1185 925 754 697 650 [RuL 3 Cl 2 ] 3054 1672 1583 1481 1438 1267 1191 914 745 698 650 The ligand and complexes display medium ir-bands near 1274-1267 cm–1 and strong band near 1191-1182 cm–1 and very strong band at 1087-1069 cm–1 and 929-914 cm–1 region attributed to (C–H) bending, (C–C) stretches and (C–P) vibrations, while (P = S) stretches are observed in the region 1169-1159 cm–1 as a strong and broad band. Which supports the participation of sulphur as donor atom17A very strong and broad band also observed in the ligand and complexes at 754-745 cm–1 attributed to (P = S) vibrations. The strong peak at 692 cm–1 and 638 cm–1 indicate the facts that the aromatic ring may be singly substituted18 as shown in table-1. NMR spectra :H NMR spectra and 13C NMR spectra of these complexes of Rhodium(I) and Ruthenium(II) with TPPS ligand have been recorded in CDCl solvent. Rhodium complex display a number of signals between 7.40 ppm to 7.72 ppm, indicate that a number of benzene rings are present in the complexes. Since the hydrogen atoms directly bonded to an aromatic ring are easily identified by P NMR spectra. These hydrogens are strongly deshielded by the aromatic ring and also absorb between 7.0 to 8.0 ppm downfield from TMS standard. Ruthenium complex also display a number of signals between 7.25 ppm to 7.75 ppm. 13C NMR spectra of the Complexes exhibit C/C, C/C, C and type absorption peaks 128.3/128.5, 131.7/131.8, 131.8, 131.9 and 132.0 indicating the presence of phenyl rings in the complexes. 13C NMR spectra of the both complexes show that the triplet peaks at 77. This is the carbon signal for deuterated chloroform (CDCl) solvent which split into three equal sized peaks by coupling with the deuterium atom. The spectra of the complex also exhibit absorption between 2.45 to 3.25 indicating the presence of electronegative chlorine atom. The ruthenium(II) complex also shows four different types of peaks range between 128-135 indicating the presence of phenyl groups as well as formation of Ru-S bond19–20. Organophosphorous compounds formed aryl (C–P) bonds between 125-140 according to William Kemp21Both the complexes also formed absorption peaks between above range confirms the presence of (C–P) bonds in the complexes. ConclusionIn the light of above discussion, particularly the metal-ligand ratio, its analytical data, IR spectra, NMR spectra and magnetic properties of ligand and complexes suggested thats rhodium(I) complex is four coordinated square planar geometry, which is the most favourable geometry of the rhodium(I) complexes, while the ruthenium(II) has trigonal bipyramidal structure. Rhcomplex is found to be diamagnetic, while RuII complex is paramagnetic. AcknowledgementThe authors thankful to Prof. Sumyo Mukherjee, Head, SAIF, IIT, Powai, Mumbai and micro analysists of the department for analysing the compounds and spectral measurements. Authors are thankful to UGC, New Delhi, for award of major Research Project. 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