Dichlorotetrakis(dimethylsulfoxide)ruthenium(II)

Last updated
Dichlorotetrakis(dimethyl­sulfoxide) ruthenium (II)
RuCl2-dmso4.PNG
RuCl2(dmso)4 (Strem).jpg
Names
Systematic IUPAC name
Ruthenium, dichlorotetrakis(sulfinylbis(methane))- (9CI)
Other names
Tetrakis(dimethylsulfoxide)dichlororuthenium(II), Dichlorotetrakis(methylsulfoxide)ruthenium, Dichlorotetrakis(sulfinylbis(methane))ruthenium
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/4C2H6OS.2ClH.Ru/c4*1-4(2)3;;;/h4*1-2H3;2*1H;/q;;;;;;+2/p-2
    Key: UMJDEUKQHKMAOI-UHFFFAOYSA-L
  • CS(=O)C.CS(=O)C.CS(=O)C.CS(=O)C.Cl[Ru]Cl
Properties
C8H24Cl2O4RuS4
Molar mass 484.51 g/mol
AppearanceVarious shades of yellow crystals
Miscible in water
Solubility Nitromethane, chloroform, dichloromethane
Structure
Octahedral coordinate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Dichlorotetrakis(dimethyl sulfoxide) ruthenium(II) describes coordination compounds with the formula RuCl2(dmso)4, where DMSO is dimethylsulfoxide. Both cis and trans isomers are known, but the cis isomer is more common. The cis isomer is a yellow, air-stable solid that is soluble in some organic solvents. These sulfoxide complexes are used in the synthesis of various ruthenium(ii) complexes. [1] They have also attracted attention as possible anti-cancer drugs.

Contents

Structure and synthesis

The cis isomer illustrates linkage isomerism for the DMSO ligand. [2] One of the two dmso ligands that are cis to both chloride ligands is O-bonded while the other three dmso ligands are S-bonded. In the trans isomer, which is also yellow, all four dmso ligands are S-bonded. The cis isomer is formed thermally, and the trans isomer is obtained by UV-irradiation of the cis isomer. [3]

Cis-fac-dichlorotetrakis(dimethyl-sulfoxide)ruthenium(II)-from-xtal-2008-3D-balls.png Trans-dichloridotetrakis(dimethyl-sulfoxide)ruthenium(II)-from-xtal-1990-3D-balls.png
cis isomertrans isomer

The complexes were first prepared in 1971 by heating DMSO solutions of ruthenium trichloride under hydrogen atmosphere. [4] Modern procedures has been developed which avoids hydrogen gas, either using ascorbic acid or refluxing DMSO to reduce the ruthenium. [3] [5] [6]

Potential applications

RuCl2(dmso)4 was identified as a potential anticancer agent in the early 1980s. [7] Continued research [8] [9] has led to the development of several related dmso-containing ruthenium compounds, some of which have undergone early-stage clinical trials. [10]

Related Research Articles

<span class="mw-page-title-main">Coordination complex</span> Molecule or ion containing ligands datively bonded to a central metallic atom

A coordination complex is a chemical compound consisting of a central atom or ion, which is usually metallic and is called the coordination centre, and a surrounding array of bound molecules or ions, that are in turn known as ligands or complexing agents. Many metal-containing compounds, especially those that include transition metals, are coordination complexes.

<span class="mw-page-title-main">Dimethyl sulfoxide</span> Organosulfur chemical compound used as a solvent

Dimethyl sulfoxide (DMSO) is an organosulfur compound with the formula (CH3)2SO. This colorless liquid is the sulfoxide most widely used commercially. It is an important polar aprotic solvent that dissolves both polar and nonpolar compounds and is miscible in a wide range of organic solvents as well as water. It has a relatively high boiling point. DMSO has the unusual property that many individuals perceive a garlic-like taste in the mouth after DMSO makes contact with their skin.

In chemistry, linkage isomerism or ambidentate isomerism is a form of isomerism in which certain coordination compounds have the same composition but differ in their metal atom's connectivity to a ligand.

<span class="mw-page-title-main">Octahedral molecular geometry</span> Molecular geometry

In chemistry, octahedral molecular geometry, also called square bipyramidal, describes the shape of compounds with six atoms or groups of atoms or ligands symmetrically arranged around a central atom, defining the vertices of an octahedron. The octahedron has eight faces, hence the prefix octa. The octahedron is one of the Platonic solids, although octahedral molecules typically have an atom in their centre and no bonds between the ligand atoms. A perfect octahedron belongs to the point group Oh. Examples of octahedral compounds are sulfur hexafluoride SF6 and molybdenum hexacarbonyl Mo(CO)6. The term "octahedral" is used somewhat loosely by chemists, focusing on the geometry of the bonds to the central atom and not considering differences among the ligands themselves. For example, [Co(NH3)6]3+, which is not octahedral in the mathematical sense due to the orientation of the N−H bonds, is referred to as octahedral.

<span class="mw-page-title-main">Metal ammine complex</span>

In coordination chemistry, metal ammine complexes are metal complexes containing at least one ammonia ligand. "Ammine" is spelled this way for historical reasons; in contrast, alkyl or aryl bearing ligands are spelt with a single "m". Almost all metal ions bind ammonia as a ligand, but the most prevalent examples of ammine complexes are for Cr(III), Co(III), Ni(II), Cu(II) as well as several platinum group metals.

<span class="mw-page-title-main">Photochromism</span> Reversible chemical transformation by absorption of electromagnetic radiation

Photochromism is the reversible change of color upon exposure to light. It is a transformation of a chemical species (photoswitch) between two forms by the absorption of electromagnetic radiation (photoisomerization), where the two forms have different absorption spectra.

<span class="mw-page-title-main">Ruthenium(III) chloride</span> Chemical compound

Ruthenium(III) chloride is the chemical compound with the formula RuCl3. "Ruthenium(III) chloride" more commonly refers to the hydrate RuCl3·xH2O. Both the anhydrous and hydrated species are dark brown or black solids. The hydrate, with a varying proportion of water of crystallization, often approximating to a trihydrate, is a commonly used starting material in ruthenium chemistry.

<span class="mw-page-title-main">Dicarbonyltris(triphenylphosphine)ruthenium(0)</span> Chemical compound

Dicarbonyltris(triphenylphosphine)ruthenium(0) or Roper's complex is a ruthenium metal carbonyl. In it, two carbon monoxide ligands and three triphenylphosphine ligands are coordinated to a central ruthenium(0) center.

<span class="mw-page-title-main">Dichlorotris(triphenylphosphine)ruthenium(II)</span> Chemical compound

Dichlorotris(triphenylphosphine)ruthenium(II) is a coordination complex of ruthenium. It is a chocolate brown solid that is soluble in organic solvents such as benzene. The compound is used as a precursor to other complexes including those used in homogeneous catalysis.

Metal acetylacetonates are coordination complexes derived from the acetylacetonate anion (CH
3
COCHCOCH
3
) and metal ions, usually transition metals. The bidentate ligand acetylacetonate is often abbreviated acac. Typically both oxygen atoms bind to the metal to form a six-membered chelate ring. The simplest complexes have the formula M(acac)3 and M(acac)2. Mixed-ligand complexes, e.g. VO(acac)2, are also numerous. Variations of acetylacetonate have also been developed with myriad substituents in place of methyl (RCOCHCOR). Many such complexes are soluble in organic solvents, in contrast to the related metal halides. Because of these properties, acac complexes are sometimes used as catalyst precursors and reagents. Applications include their use as NMR "shift reagents" and as catalysts for organic synthesis, and precursors to industrial hydroformylation catalysts. C
5
H
7
O
2
in some cases also binds to metals through the central carbon atom; this bonding mode is more common for the third-row transition metals such as platinum(II) and iridium(III).

<span class="mw-page-title-main">Pentaamine(dinitrogen)ruthenium(II) chloride</span> Chemical compound

Pentaamine(nitrogen)ruthenium(II) chloride is an inorganic compound with the formula [Ru(NH3)5(N2)]Cl2. It is a nearly white solid, but its solutions are yellow. The cationic complex is of historic significance as the first compound with N2 bound to a metal center. [Ru(NH3)5(N2)]2+ adopts an octahedral structure with C4v symmetry.

<span class="mw-page-title-main">Cyclopentadienyliron dicarbonyl dimer</span> Chemical compound

Cyclopentadienyliron dicarbonyl dimer is an organometallic compound with the formula [(η5-C5H5)Fe(CO)2]2, often abbreviated to Cp2Fe2(CO)4, [CpFe(CO)2]2 or even Fp2, with the colloquial name "fip dimer". It is a dark reddish-purple crystalline solid, which is readily soluble in moderately polar organic solvents such as chloroform and pyridine, but less soluble in carbon tetrachloride and carbon disulfide. Cp2Fe2(CO)4 is insoluble in but stable toward water. Cp2Fe2(CO)4 is reasonably stable to storage under air and serves as a convenient starting material for accessing other Fp (CpFe(CO)2) derivatives (described below).

Ruthenium anti-cancer drugs are coordination complexes of ruthenium complexes that have anticancer properties. They promise to provide alternatives to platinum-based drugs for anticancer therapy. No ruthenium anti-cancer drug has been commercialized.

A metal carbido complex is a coordination complex that contains a carbon atom as a ligand. They are analogous to metal nitrido complexes. Carbido complexes are a molecular subclass of carbides, which are prevalent in organometallic and inorganic chemistry. Carbido complexes represent models for intermediates in Fischer–Tropsch synthesis, olefin metathesis, and related catalytic industrial processes. Ruthenium-based carbido complexes are by far the most synthesized and characterized to date. Although, complexes containing chromium, gold, iron, nickel, molybdenum, osmium, rhenium, and tungsten cores are also known. Mixed-metal carbides are also known.

<span class="mw-page-title-main">Tris(acetonitrile)cyclopentadienylruthenium hexafluorophosphate</span> Chemical compound

Tris(acetonitrile)cyclopentadienylruthenium hexafluorophosphate is an organoruthenium compound with the formula [(C5H5)Ru(NCCH3)3]PF6, abbreviated [CpRu(NCMe)3]PF6. It is a yellow-brown solid that is soluble in polar organic solvents. The compound is a salt consisting of the hexafluorophosphate anion and the cation [CpRu(NCMe)3]+. In coordination chemistry, it is used as a source of RuCp+ for further derivitization. In organic synthesis, it is a homogeneous catalyst. It enables C-C bond formation and promotes cycloadditions. The cyclopentadienyl ligand (Cp) is bonded in an η5 manner to the Ru(II) center.

DNA-binding metallo-intercalators are positively charged, planar, polycyclic, aromatic compounds that unwind the DNA double helix and insert themselves between DNA base pairs. Metallo-intercalators insert themselves between two intact base pairs without expelling or replacing the original nitrogenous bases; the hydrogen bonds between the nitrogenous bases at the site of intercalation remain unbroken. In addition to π-stacking between the aromatic regions of the intercalator and the nitrogenous bases of DNA, intercalation is stabilized by van der Waals, hydrophobic, electrostatic, and entropic interactions. This ability to bind to specific DNA base pairs allows for potential therapeutic applications of metallo-intercalators.

RAPTA is a class of experimental cancer drugs. They consist of a central ruthenium(II) atom complexed to an arene group, chlorides, and 1,3,5-triaza-7-phosphaadamantane (PTA) forming an organoruthenium half-sandwich compound. Other related ruthenium anti-cancer drugs include NAMI-A, KP1019 and BOLD-100.

<i>cis</i>-Dichlorobis(bipyridine)ruthenium(II) Chemical compound

cis-Dichlorobis(bipyridine)ruthenium(II) is the coordination complex with the formula RuCl2(bipy)2, where bipy is 2,2'-bipyridine. It is a dark green diamagnetic solid that is a precursor to many other complexes of ruthenium, mainly by substitution of the two chloride ligands. The compound has been crystallized as diverse hydrates.

<span class="mw-page-title-main">Transition metal thioether complex</span>

Transition metal thioether complexes comprise coordination complexes of thioether (R2S) ligands. The inventory is extensive.

<span class="mw-page-title-main">Transition metal sulfoxide complex</span> Class of coordination compounds containing sulfoxide ligands)

A transition metal sulfoxide complex is a coordination complex containing one or more sulfoxide ligands. The inventory is large.

References

  1. Alessio, Enzo (2004-09-01). "Synthesis and Reactivity of Ru-, Os-, Rh-, and Ir-Halide−Sulfoxide Complexes". Chemical Reviews. 104 (9): 4203–4242. doi:10.1021/cr0307291. ISSN   0009-2665.
  2. Enzo Alessio (2004). "Synthesis and reactivity of Ru-, Os-, Rh-, and Ir-halide-sulfoxide compounds". Chem. Rev. 104 (9): 4203–4242. doi:10.1021/cr0307291. PMID   15352790.
  3. 1 2 I. Bratsos; E. Alessio (2010). Ruthenium(II) Chloro Complexes of dimethylsulfoxide. Inorganic Syntheses. Vol. 35. pp. 148–152. doi:10.1002/9780470651568.ch8.
  4. B. R. James; E. Ochiai; G.I. Rempel (1971). "Ruthenium (II) halide dimethylsulphoxide complexes from hydrogenation reactions". Inorganic and Nuclear Chemistry Letters. 7 (8): 781–784. doi:10.1016/0020-1650(71)80091-0.
  5. Nagy, E. M.; Pettenuzzo, A. (2012). "Ruthenium(II/III)-Based Compounds with Encouraging Antiproliferative Activity against Non-small-Cell Lung Cancer". Chemistry: A European Journal . 18 (45): 14464–14472. doi:10.1002/chem.201202171. PMID   23012112.
  6. Abdou, Hanan E.; Mohamed, Ahmed A.; Fackler, John P.; Ghimire, Mukunda M.; Omary, Mohammad A.; Schilter, David; Rauchfuss, Thomas B.; Denny, Jason A.; Darensbourg, Marcetta Y. (2018-07-27), Power, Philip P. (ed.), "SYNTHESIS OF SELECTED TRANSITION METAL AND MAIN GROUP COMPOUNDS WITH SYNTHETIC APPLICATIONS", Inorganic Syntheses (1 ed.), Wiley, vol. 37, pp. 155–204, doi:10.1002/9781119477822.ch8, ISBN   978-1-119-47782-2 , retrieved 2024-01-30
  7. Sava, Gianni; Giraldi, Tullio; Mestroni, Giovanni; Zassinovich, Grazia (July 1983). "Antitumor effects of rhodium(I), iridium(I) and ruthenium(II) complexes in comparison with cis-dichlorodiammino platinum(II) in mice bearing Lewis lung carcinoma". Chemico-Biological Interactions. 45 (1): 1–6. doi:10.1016/0009-2797(83)90037-6. PMID   6683595.
  8. Coluccia, Mauro; Sava, Gianni; Loseto, Francesco; Nassi, Anna; Boccarelli, Angela; Giordano, Domenico; Alessio, Enzo; Mestroni, Giovanni (January 1993). "Anti-leukaemic action of RuCl2(DMSO)4 isomers and prevention of brain involvement on P388 leukaemia and on subline". European Journal of Cancer. 29 (13): 1873–1879. doi:10.1016/0959-8049(93)90541-M. PMID   8260245.
  9. Bratsos, I; Serli, B; Zangranko, E; Katsaros, N; Alessio, E. (2007). "Replacement of chlorides with dicarboxylate ligands in anticancer active Ru(II)-DMSO compounds: A new strategy that might lead to improved activity". Inorg. Chem. 46 (3): 975–992. doi:10.1021/ic0613964. PMID   17257042.
  10. Enzo Alessio, Bentham Science Publisher; Giovanni Mestroni, Bentham Science Publisher; Alberta Bergamo, Bentham Science Publisher; Gianni Sava, Bentham Science Publisher (1 November 2004). "Ruthenium Antimetastatic Agents". Current Topics in Medicinal Chemistry. 4 (15): 1525–1535. doi:10.2174/1568026043387421. PMID   15579094.