Pentaamine(dinitrogen)ruthenium(II) chloride

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Pentaamine(dinitrogen)­ruthenium(II) chloride
RuA5N2.png
Names
IUPAC name
pentaamminedinitrogenruthenium (II) chloride
Identifiers
3D model (JSmol)
  • InChI=1S/2ClH.N2.5H3N.Ru/c;;1-2;;;;;;/h2*1H;;5*1H3;/q;;;;;;;;+2/p-2
    Key: VLZPOOHIDLPMKN-UHFFFAOYSA-L
  • [Cl-].N#[N+][Ru-4]([NH3+])([NH3+])([NH3+])([NH3+])[NH3+].[Cl-]
Properties
H15N7Cl2Ru
Molar mass 285.14 g/mol
Appearancecolorless solid
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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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. [1] [2] [Ru(NH3)5(N2)]2+ adopts an octahedral structure with C4v symmetry. [3]

Contents

Preparation and properties

Pentaamine(nitrogen)ruthenium(II) chloride is synthesized in an aqueous solution from pentaamminechlororuthenium(III) chloride, sodium azide, and methanesulfonic acid: [4]

[Ru(NH3)5Cl]Cl2 + NaN3 → [Ru(NH3)5N2]Cl2 + ...

If it is to be used in situ, the cation can be made more conveniently from ruthenium(III) chloride and hydrazine hydrate: [4]

RuCl3 + 4 N2H4 → [Ru(NH3)5N2]2+ + ...

This N2 complex is stable in aqueous solution and has a relatively low ligand exchange rate with water. Being a d6 complex, the Ru-N bond is stabilized by the pi backbonding, the donation of metal d-electrons into the N2 π* orbitals. [5] The related metal ammine complex [Os(NH3)5(N2)]2+ is also known.

Reactions

The dinitrogen ligand is not reduced by aqueous sodium borohydride. [6] Nearly all known reactions of this compound are displacement reactions. Pentaamine(halogen)ruthenium(II) halides can be synthesized by treating [Ru(NH3)5N2]2+ with halide sources: [4]

[Ru(NH3)5N2]2+ + X → [Ru(NH3)5X]+ + N2

[Ru(NH3)5N2]2+ forms the symmetrically bridging symmetrical dinitrogen complex [(NH3)5Ru-NN-Ru(NH3)5]4+. [7] [8]

Related Research Articles

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<span class="mw-page-title-main">Zinc chloride</span> Chemical compound

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Abiological nitrogen fixation describes chemical processes that fix (react with) N2, usually with the goal of generating ammonia. The dominant technology for abiological nitrogen fixation is the Haber process, which uses an iron-based heterogeneous catalysts and H2 to convert N2 to NH3. This article focuses on homogeneous (soluble) catalysts for the same or similar conversions.

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

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References

  1. Allen, A. D.; Senoff, C. V. (1965). "Nitrogenopentammineruthenium(II) Complexes". Chemical Communications (24): 621. doi:10.1039/C19650000621.
  2. Senoff, Caesar V. (1990). "The Discovery of [Ru(NH3)5N2]2+: A Case of Serendipity and the Scientific Method". Journal of Chemical Education. 67 (5): 368. Bibcode:1990JChEd..67..368S. doi:10.1021/ed067p368.
  3. Fergusson, J. E.; Love, J. L.; Robinson, Ward T. (1972). "Crystal and Molecular Structure of Dinitrogenpentaammineosmium(II) chloride, [Os(NH3)5N2]Cl2, and Related Ruthenium Complexes". Inorganic Chemistry. 11 (7): 1662–1666. doi:10.1021/ic50113a042.
  4. 1 2 3 Allen, A. D., Bottomley, F., Harris, R. O., Reinsalu, V. P., Senoff, C. V. "Pentaammine(Nitrogen)Ruthenium(II) Salts and Other Ammines of Ruthenium" Inorganic Syntheses, 2007, volume 12, pp. 2-8. doi : 10.1002/9780470132432.ch1
  5. Taube, H. "Chemistry of Ruthenium(II) and Osmium(II) Ammines" Pure and Applied Chemistry, 1979, volume 51, p. 901–12. doi : 10.1351/pac197951040901
  6. J. Chatt, R. L. Richards, J. F. Fergusson and J. L. Love, "The reduction of nitrogen complexes" Chem. Commun. 1968, 1522. doi : 10.1039/C19680001522
  7. Harrison, D. F.; Weissberger, E.; Taube, H. (1968). "Binuclear Ion Containing Nitrogen as a Bridging Group". Science. 159 (3812): 320–322. Bibcode:1968Sci...159..320H. doi:10.1126/science.159.3812.320. PMID   5634502. S2CID   39569679.
  8. Chatt, J. (1970). "Molecular Nitrogen as a Ligand". Pure and Applied Chemistry. 24 (2): 425–442. doi:10.1351/pac197024020425.