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Serendipitous Formation of First Neutral Mononuclear Rh(II) Complex of 1, 10-Phenanthroline


Affiliations
1 Department of Chemistry, Kakatiya University, Warangal
2 Centre for Pharmaceutical Science, Institute of Science and Technology, JNTU, Hyderabad
3 Department of Chemistry, Satavahana University, Karimnagar, 505 001
     

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The reaction of RhCl3 with 1,10-phenanthroline followed by a carboxyl functionalized tertiaryphosphine in refluxing ethanol led to serendipitous formation of a first neutral mononuclear Rh(II) complex of 1,10-phenanthroline as [Rh(II)Cl<SUB>2</SUB>(1,10-phen)2] without incorporating the phosphine. This incident was evidenced by elemental analysis, single crystal X-ray diffraction, EPR and Mass spectroscopic studies.

Keywords

Rhodium, Tertiary phosphines, 1, 10-phenanthroline, Reduction
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  • Ungváry F. Application of transition metals in hydroformylation: Annual survey covering the year 2005. Coord. Chem. Rev. 2007; 251: 2072-2086.
  • Erre G, Enthaler S, Junge K, Gladiali S and Beller M. Synthesis and application of chiral monodentate phosphines in asymmetric hydrogenation. Coord. Chem. Rev. 2008; 252: 471-491.
  • Shaughnessy K H. Hydrophilic Ligands and Their Application in Aqueous-Phase Metal-Catalyzed Reactions. Chem. Rev. 2009; 109: 643-710.
  • Saidi O, Liu S and Xiao J. Effects of ligands on the rhodiumcatalyzed hydroformylation of acrylate. J. Mol. Cat. A Chemical. 2009; 305: 130-134.
  • Barry C G, Turney E C, Day C S, Saluta G, Kucera G L and Bierbach U. Thermally Inert Metal Ammines as Light-Inducible DNA-Targeted Agents. Synthesis, Photochemistry, and Photobiology of a Prototypical Rhodium(III)-Intercalator Conjugate. Inorg. Chem. 2002; 41: 7159-7169.
  • Terbrueggen R H, Johann T W and Barton J K. Functionalized Rhodium Intercalators for DNA Recognition. Inorg. Chem. 1998; 37: 6874-6883.
  • Rivas A B, Pérez-Torrente J J, Pardey A J, Masdeu-Bultó A M, Diéguez M and Oro L A. Hydroformylation of oct-1-ene catalyzed by dinuclear gem-dithiolato-bridged rhodium(I) complexes and phosphorus donor ligands. J. Mol. Cat. A Chemical. 2009; 300: 121- 131.
  • Toganoh M, Harada N and Furuta H. Hydrogen-bonding network in new scorpionate-type ligand composed of pyridine/pyrrole hybrid and anion-binding behavior of the corresponding rhodium complexes in alkyne cyclotrimerization reaction. J. Organomet. Chem. 2008; 693: 3141-3150.
  • Schaub T, Diskin-Posner Y, Radius U and Milstein D. Synthesis, Structure, and Reactivity of Rhodium and Iridium Complexes of the Chelating Bis-Sulfoxide tBuSOC 2H 4SO tBu. Selective O-H Activation of 2-Hydroxy- isopropyl-pyridine. Inorg. Chem. 2008; 47: 6502-6512.
  • Shibue M, Hirotsu M, Nishioka T and Kinoshita I. Ruthenium and Rhodium Complexes with Thiolate-Containing Pincer Ligands Produced by C-S Bond Cleavage of Pyridyl-Substituted Dibenzothiophenes. Organometallics. 2008; 27: 4475-4483.
  • Blacker A J, Duckett S B, Grace J, Perutz R N and Whitwood A C. Reactivity, Structures, and NMR Spectroscopy of Half-Sandwich Pentamethylcyclopentadienyl Rhodium Amido Complexes Relevant to Transfer Hydrogenation. Organometallics. 2009; 28: 1435-1446.
  • Ravinder V, Hemling H, Shumann H and Blum J. A new synthesis of hydrophilic carboxylated arylphosphines. Synth. Commun. 1992; 22: 841-851.
  • Ravinder V, Hemling H, Shumann H and Blum J. A novel convenient synthesis of arylphosphines containing reactive functional groups. Synth. Commun. 1992; 22: 1453-1459.
  • Schumann H, Ravindar V, Meltser L, Baidossi W, Sasson Y and Blum J. Effect of the CO2H groups of carboxylated triarylphosphines on (COD)RhCl(PAr3)-catalyzed isomerization of 1-octen-3-ol under phase transfer conditions. J. Mol. Cat. A Chemical. 1997; 118: 55-61.
  • Schumann H, Hemling H, Ravindar V, Badrieh Y and Blum J. Effects of changes in the ligands on the skeleton and the catalytic activity of some new rhodium complexes with pyrazolato moieties. J. Organomet. Chem. 1994; 469: 213-219.
  • Sarangapani M and Ravinder V. Reactivity of [{(6 -pcymene) RuCl(µ-Cl)}2] towards some N-heterocyclics and tertiary phosphines. Ind. J. Chem. 2002; 41(A): 2060-2064.
  • Sarangapani M, Chandrasekhar V and Ravinder V. Synthesis and characterization of (6-p-cymene) RuII complexes containing N, N O donor ligands and tertiary phosphines. J. Ind. Chem. Soc. 2005; 82: 497-502.
  • Usharani P, Muralidhar Reddy P, Sarangapani M and Ravinder V. Synthesis, spectral and catalytic hydrogenation studies of palladium(II) complexes containing substituted tertiary phosphines. J. Ind. Chem. Soc. 2007; 84: 122-129.
  • Muralidhra Reddy P, Shanker K, Rohini R, Sarangapani M and Ravinder V. Substituted tertiary phosphine Ru(II) organometallics: Catalytic utility on the hydrolysis of etofibrate in pharmaceuticals. Spectrochim. Acta A. 2008; 70: 1231-1237.
  • Chandrasekhar V, Sarangapani M, Shanker K and Ravinder V. Synthesis, characterization and hydroformylation activity of 7- azaindolate-bridged dinuclear rhodium(I)phosphines with pendant polar-groups. Appl. Organomet. Chem. 2009; 23: 460-466.
  • Rosenberg B, VanCamp L and Trosko J E. Platinum compounds: a new class of potent antitumour agents. Nature. 1969; 222: 385-386.
  • Scharwitz M A, Ott I, Geldmacher Y, Gust R & Sheldrick W S. Cytotoxic half-sandwich rhodium(III) complexes: Polypyridyl ligand influence on their DNA binding properties and cellular uptake. J. Organomet. Chem. 2008; 693: 2299-2309.
  • Menon E L, Perera R, Navarro M, Kuhn R J & Morrison H. Phototoxicity against Tumor Cells and Sindbis Virus by an Octahedral Rhodium Bisbipyridyl Complex and Evidence for the Genome as a Target in Viral Photoinactivation. Inorg. Chem. 2004; 43: 5373-5381.
  • Muir M M, Gomez G M, Muir J A and Sanchez S. Structure of trans-dibromotetrakis(pyridine)rhodium(III) bromide hexahydrate. Acta Cryst. 1987; C43: 839-842.
  • Cini R, Cavaglioni A and Tiezzi E. X-ray structures of transdichloro( 4-methylpyrimidine) ( 1-phenyl)bis(pyridine)rhodium(III) hydrate and trans-dichloro(phenyl)tris(triphenylstibine)rhodium(III) ethylacetate solvate. Molecular orbital analysis of trans-dichloro (4- methylpyrimidine)( 1-phenyl)bis(pyridine)rhodium(III). Polyhedron. 1999; 18: 669-678.
  • Mintert M and Sheldrick W S. Dinuclear Rh(I,I) and Rh(II,II) complexes containing bridging asymmetrically 2,7-disubstituted naphthyridines. Inorg. Chim. Acta. 1997; 254: 93-98.
  • Feller M, Ben-Ari E, Gupta T, Shimon L J W, Leitus G, Diskin- Posner Y, Weiner L and Milstein D. Mononuclear Rh(II) PNP-Type Complexes. Structure and Reactivity. Inorg. Chem. 2007; 46: 10479- 10490.
  • Exarchos G and Robinson S D. Observations concerning the constitution of some ‘rhodium(II) dithiocarbamato complexes’. Polyhedron. 2000; 19: 123-124.
  • Willems S T H, Russcher J C, Budzelaar P H M, de Bruin B, de Gelder R, Smits J M M and Gal A W. Spontaneous disproportionation of rhodium(I) bisoxazolinates to rhodium(II). Chem. Commun. 2002; 148-149.
  • JI Z, Shan Y, Guadalupe A R and Huang S D. Crystal structure of cisdichlorobis( 1,10-phenanthroline)rhodium(III) perchlorate. Zeitschrift für Kristallographie. 1999; 214: 387-388.
  • Kulasingam G C, McWhinnie W R and Miller J D. The mechanism of formation and the stereochemistry of mono- and bis-complexes of rhodium(III) with 1,10-phenanthroline. J. Chem. Soc. A. 1969; 521- 524.
  • Indelli M T, Carioli A and Scandola F. Excited-state absorption of tris(phenanthroline)rhodium(III). A handle on the excited-state behavior of a powerful photochemical oxidant. J. Phys. Chem. 1984; 88: 2685-2686.
  • Loganathan D, Rodriguez J H and Morrison H. Photoaquation of Methylated cis-Dichlorobis(1,10-phenanthroline)rhodium(III)chloride Compounds by Direct Population of a Photoactive Triplet Excited State. J. Am. Chem. Soc. 2003; 125: 5640-5641.
  • Glowiak T, Pasternak H and Pruchnik F. Structure of the binuclear rhodium(II) complex dichloro-di-µ-formato-bis(1,10-phenanthroline) dirhodium(II). Acta Cryst. 1987; C43: 1036-1038.
  • Pruchnik F P, Bien M and Lachowicz T. Properties of Binuclear Rhodium(II) Complexes and Their Antibacterial Activity. Metal- Based Drugs. 1996; 3: 185-195.
  • Menglet D, Bond A M, Coutinho K, Dickson R S, Lazarev G G, Olsen S A and Pilbrow J R. EPR, Electronic Spectra, and Electron Transfer Properties of the 17 Electron Carbonylhydrotris (triphenylphosphine)rhodium(II) Cation. J. Am. Chem. Soc. 1998; 120: 2086-2089.
  • Vrielinck H, Callens F and Matthys P. Reinterpretation of temperature-induced dynamical behavior in the EPR spectrum of Rh2+ centers in AgCl. Physical Review B. 2003; 68: 212405.
  • Sabbe K, Vrielinck H, Callens F, Boesman E, Vercammen H, Ka H, Goovaerts E, Bouwen A and Schoemaker D. Study of strongly overlapping Rh2+ EPR spectra by high-resolution magnetic resonance techniques. J. Chem. Soc. Faraday Trans. 1998; 94: 2993-2997.

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  • Serendipitous Formation of First Neutral Mononuclear Rh(II) Complex of 1, 10-Phenanthroline

Abstract Views: 315  |  PDF Views: 2

Authors

Shravankumar Kankala
Department of Chemistry, Kakatiya University, Warangal
Prasad Gundepaka
Centre for Pharmaceutical Science, Institute of Science and Technology, JNTU, Hyderabad
Vinutha Chakilam
Department of Chemistry, Kakatiya University, Warangal
Kavitha Natte
Department of Chemistry, Kakatiya University, Warangal
Hanmanthu Guguloth
Department of Chemistry, Kakatiya University, Warangal
Ravinder Vadde
Department of Chemistry, Kakatiya University, Warangal
Chandra Sekhar Vasam
Department of Chemistry, Satavahana University, Karimnagar, 505 001
Mukkanti Kagga
Centre for Pharmaceutical Science, Institute of Science and Technology, JNTU, Hyderabad

Abstract


The reaction of RhCl3 with 1,10-phenanthroline followed by a carboxyl functionalized tertiaryphosphine in refluxing ethanol led to serendipitous formation of a first neutral mononuclear Rh(II) complex of 1,10-phenanthroline as [Rh(II)Cl<SUB>2</SUB>(1,10-phen)2] without incorporating the phosphine. This incident was evidenced by elemental analysis, single crystal X-ray diffraction, EPR and Mass spectroscopic studies.

Keywords


Rhodium, Tertiary phosphines, 1, 10-phenanthroline, Reduction

References