The kinetics and mechanism of the ligand substitution reaction of aquapentacyanoruthenate(II) with d-penicillamine in aqueous medium

The kinetics of the formation of the light orange–coloured complex [Ru(CN)5D-PA]3− are studied spectrophotometrically through substitution of a coordinated H2O molecule in aquapentacyanoruthenate(II) [Ru(CN)5OH2]3− by interaction with D-penicillamine [D-PA] in aqueous medium at 490 nm (λmax of [Ru(CN)5D-PA]3−). The reaction is monitored under pseudo-first-order conditions, taking [D-PA] in excess over [Ru(CN)5OH23−]. The effects of various reaction parameters on the rate of the reaction are investigated. Experimental observations reveal that the variation in [D-PA] obeyed the first-order rate law while it is found to be invariant with [Ru(CN)5OH23−] in the whole experimental range. With ionic strength variation, as the reaction advances a decrease in the reaction rate is noticed. The product stoichiometry is assigned as 1:1. The ease of substitution at an H2O molecule in [Ru(CN)5OH23−] is considered on the basis of the electronic effect generated through interactions of the M–OH2 bond. A provisional mechanism based on the calculated results is proposed based on the slowest step of the reaction.

• Publication year

  2020

• Venue

  Journal of Chemical Research

• Publication date

  2020-11-24

• Fields of study

  Chemistry

• Identifiers
  DOI 10.1177/1747519820961015
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar

• No claims are published for this paper.

• No concepts are published for this paper.

• Octahedral rhodium(III) complexes as kinase inhibitors: Control of the relative stereochemistry with acyclic tridentate ligands.

  2015cited by this paper
• Probing Chiral Recognition of Enzyme Active Sites with Octahedral Iridium(III) Propeller Complexes

  2015cited by this paper
• Group 9 organometallic compounds for therapeutic and bioanalytical applications.

  2014cited by this paper
• Approaching tumour therapy beyond platinum drugs: status of the art and perspectives of ruthenium drug candidates.

  2012cited by this paper
• The art of filling protein pockets efficiently with octahedral metal complexes.

  2012cited by this paper
• Kinetics and Mechanism of Formation of [Fe(CN)5D-PA]3− by Ligand Substitution Reaction in the Presence of Surfactant Micelle in Acidic Media

  2012cited by this paper
• The kinetics and mechanism of the substitution reactions of the aquapentacyanoruthenate(II) ion with naphthalene-substituted ligands in aqueous medium

  2011cited by this paper
• Polynuclear ruthenium, osmium and gold complexes. The quest for innovative anticancer chemotherapeutics.

  2011cited by this paper
• Organometallic complexes: new tools for chemotherapy.

  2010cited by this paper
• Metal complexes as protein kinase inhibitors.

  2010cited by this paper
• Organometallic Anticancer Compounds

  2010cited by this paper
• Iridium complex with antiangiogenic properties.

  2010cited by this paper
• Targeting proteins with metal complexes.

  2009cited by this paper
• Platinum and Other Heavy Metal Compounds in Cancer Chemotherapy: molecular mechanisms and clinical applications

  2009cited by this paper
• Ruthenium Drugs for Cancer Chemotherapy: An Ongoing Challenge to Treat Solid Tumours

  2009cited by this paper
• Kinetic and mechanistic study of the mercury(II)-catalyzed substitution of cyanide in hexacyanoruthenate(II) by pyrazine

  2009cited by this paper
• The Kinetics and Mechanism of Ruthenium(III)-Catalyzed Oxidation of Tris(2-amino ethyl)amine by Hexacyanoferrate(III) in Aqueous Alkaline Medium

  2008cited by this paper
• Designing biological systems.

  2007cited by this paper
• Ruthenium complexes as anticancer agents.

  2006cited by this paper
• D-penicillamine adsorption on gold: an in situ ATR-IR spectroscopic and QCM study.

  2006cited by this paper
• EPR spectroscopy as a probe of metal centres in biological systems.

  2006cited by this paper
• Synthesis and Evaluation of Long-Acting D-Penicillamine Derivatives

  2005cited by this paper
• A sequential injection spectrophotometric method for the determination of penicillamine in pharmaceutical products by complexation with iron(III) in acidic media.

  2003cited by this paper
• Specific determination of cysteine and penicillamine through cyclization to 2-thioxothiazolidine-4-carboxylic acids.

  2002cited by this paper
• Spectrophotometric Determination of Biologically Active Thiols with Eosin, Silver(I) and Adenine

  2002cited by this paper
• Transport of a neurotoxicant by molecular mimicry: the methylmercury-L-cysteine complex is a substrate for human L-type large neutral amino acid transporter (LAT) 1 and LAT2.

  2002cited by this paper
• Kinetics of formation, dissociation and equilibrium constants of pentacyanoaquoruthenate(II) with heterocycles

  2000cited by this paper
• The stability of palladium(II) complexes with sulphur-containing ligands

  2000cited by this paper
• Spectrophotometric estimation of D-penicillamine in bulk and dosage forms using 2,6-dichloroquinone-4-chlorimide (DCQ).

  1999cited by this paper
• Determination of stability constants of Fe(II), Co(II) and Cu(II)-nitrilotriacetate-penicillamine mixed complexes by electrophoresis.

  1998cited by this paper
• Electrochemical Investigations of the Nickel(II)-Penicillamine System. Inert and Labile Complexes Detected by Polarography

  1998cited by this paper
• High‐Sensitive Spectrophotometric Determination of Micromolar Concentrations of D‐Penicillamine by Means of a Coupled Redox—Complexation Reaction.

  1997cited by this paper
• Feasibility of a limiting D mechanism for complex formation and ligand substitution reactions of pentacyanoferrate(II)

  1992cited by this paper
• Substitution reactions at pentacyanoferrate(II) complexes: linear free-energy relationships in mixed solvents

  1991cited by this paper
• Nitrosyl–nitrite interconversion in pentacyanoruthenate(II) complexes

  1991cited by this paper
• Radical reductions of Cu(II)-penicillamine complexes: Evidence for a Cu(II)-disulphide anion intermediate

  1991cited by this paper
• Chirality in antirheumatic drugs.

  1991cited by this paper
• Kinetics of electron-transfer reactions involving the hexacyanoruthenate(4-/3-) couple in aqueous media

  1990cited by this paper
• Electronic d-d spectra and ligand-dissociation rates of pentacyanoruthenate(II) ions

  1987cited by this paper
• Pentacyanoruthenate(II)-pentaammineruthenium(II/III) binuclear complexes bridged by cyanogen, cyanide, and 4,4'-bipyridine

  1987cited by this paper
• The limiting dissociative mechanism for substitution at thed6 centres molybdenum(O), iron(II), and cobalt(III): Kinetics of substitution at the pentacyano-4-Cyanopyridineferrate(II) anion and at 4-cyanopyridinemolybdenum(I) pentacarbonyl

  1987cited by this paper
• Kinetics and mechanism of the substitution reactions of the pentacyanoaquoruthenate(II) ion with nitrogen heterocycles in aqueous media

  1986cited by this paper
• Metal-to-ligand charge-transfer spectra of pentacyanoruthenate(II) complexes of aromatic nitrogen heterocycles

  1983cited by this paper
• Pentacyanoferrate(II) complexes of amino acids

  1982cited by this paper
• Kinetics of the formation and dissociation of pentacyanoferrate(II) complexes of cysteine, penicillamine, glutathione, and 2-mercaptoethylamine

  1981cited by this paper
• Influence of unithiol, d-penicillamine, and cysteine on the biological effects of bradykinin and the activity of carboxypeptidase N and peptidyl dipeptidase

  1981cited by this paper
• Acid dissociation and metal complex formation constants of penicillamine, cysteine, and antiarthritic gold complexes at simulated biological conditions.

  1979cited by this paper
• Stoichiometry and kinetics of the substitution-controlled oxidation of pentacyanoaquoiron(II) species by hydrogen peroxide and by tert-butyl hydroperoxide in aqueous sodium perchlorate solution

  1976cited by this paper
• Metal complexes of sulphur-containing amino acids

  1972cited by this paper
• Handbook of Chemistry and Physics

  1970cited by this paper
• Nature of the intermediate in unimolecular octahedral aquation

  1968cited by this paper

• No citing papers are available for this paper.