Pentacarbonylhydridomanganese

In this article, we are going to delve into the fascinating world of Pentacarbonylhydridomanganese, exploring its different facets and relevant aspects that make it a topic of general interest. From its origins to the present, Pentacarbonylhydridomanganese has been the subject of study, debate and controversy, arousing the curiosity and fascination of people around the world. Along these lines, we will immerse ourselves in its history, characteristics and evolution, with the purpose of providing a comprehensive and enriching vision about Pentacarbonylhydridomanganese, inviting the reader to reflect and deepen their understanding.
Pentacarbonylhydridomanganese
Pentacarbonylhydridomanganese
Pentacarbonylhydridomanganese
Names
Other names
Hydrogen pentacarbonylmanganate(−I) (7CI); Manganese, pentacarbonylhydro- (8CI); Hydridomanganese pentacarbonyl; Hydridopentacarbonylmanganese; Manganese pentacarbonyl hydride; Pentacarbonylhydromanganese; Pentacarbonylmanganese hydride
Identifiers
3D model (JSmol)
ChemSpider
  • InChI=1S/5CO.Mn.H/c5*1-2;;
    Key: SKOPWNLHPUYPLV-UHFFFAOYSA-N
  • O=C=(=C=O)(=C=O)(=C=O)=C=O
Properties
HMn(CO)5
Molar mass 195.99799 g/mol
Appearance At room temperature, it is liquid and colorless. Below its melting point, it may be sublimed in vacuum.[1]
Acidity (pKa) 7.1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa).
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Pentacarbonylhydridomanganese is an organometallic compound with formula HMn(CO)5. This compound is one of the most stable "first-row" transition metal hydrides.

Preparation

It was first reported in 1931.[2] Of the several ways to produce this compound,[3] is the protonation of the pentacarbonyl manganate anion. The latter is formed from reduction of dimanganese decacarbonyl, e.g., with superhydride:

2 LiHB(C2H5)3 + Mn2(CO)10 → 2 LiMn(CO)5 + H2 + 2 B(C2H5)3
Li[Mn(CO)5] + CF3SO3H → HMn(CO)5 + CF3SO3Li

Salts of −
 can be isolated as crystalline PPN+
 (μ-nitrido—bis-(triphenylphosphorus)) salt, which is smoothly protonated by CF
3SO
3H.[3]

PPN + CF
3SO
3H → HMn(CO)5 + PPN+
CF
3SO−
3

This compound can also be formed by the hydrolysis of pentacarbonyl(trimethylsilyl)manganese:[4]

(CO)5MnSiMe3 + H2O → HMn(CO)5 + Me3SiOH (Me = CH3)

Structure and properties

The structure of HMn(CO)5 has been studied by many methods including X-ray diffraction, neutron diffraction, and electron diffraction.[5] HMn(CO)5 can be related to the structure of a hexacarbonyl complex such as Mn(CO)+
6, and therefore has similar properties.[6] The compound has octahedral symmetry,[7] its molecular point group is C4v and the H-Mn bond length is 1.44 ± 0.03 Å.[6] Gas phase electron diffraction analysis confirms these conclusions.

Main reactions

The pKa of HMn(CO)5 in water is 7.1.[8] It is thus comparable to hydrogen sulfide, a common inorganic acid, in its acidity.

A common reaction involving HMn(CO)5 is substitution of the CO ligands by organophosphines, as occurs both thermally and photochemically. In this way the many derivatives form of the type HMn(CO)5-x(PR3)x.[9] (R here need not be a purely hydrocarbon component; it may, for instance, be OEt, where Et = ethyl group.)

HMn(CO)5 can be used to reduce olefins and other organic compounds, as well as metal halides.[3]

It can be methylated with diazomethane.[1]

HMn(CO)5 + CH2N2 → Mn(CO)5CH3 + N2

Notes

References

  1. ^ a b Eley, D.D.; Pines, Herman; Weisz, P.B. Advances In Catalysis. 32. 385. ISBN 978-0-12-007832-5
  2. ^ Hieber, W.; Leutert, F. (1931-04-01). "Zur Kenntnis des koordinativ gebundenen Kohlenoxyds: Bildung von Eisencarbonylwasserstoff". Naturwissenschaften (in German). 19 (17): 360–361. doi:10.1007/BF01522286. ISSN 1432-1904.
  3. ^ a b c Hunter, Alan D; Bianconi, Larry J; DiMuzio, Steven J; Braho, Dianne L. Synthesis and Structure- Property Relationships in η6-Arene) Cr(CO)3 Chemistry: From Guided Experiments to Discovery Research. J. Chem. Educ. 75. 1998. 891. doi:10.1021/ed075p891
  4. ^ Finn, M.G. Pentacarbonyl(trimethylsilyl)manganese. Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rp022s
  5. ^ Kukolich, Stephen G.; Sickafoose, Shane M. (1994-03-01). "Microwave Spectrum and Molecular Structure for Manganese Pentacarbonyl Hydride". Inorganic Chemistry. 33 (6): 1217–1219. doi:10.1021/ic00084a041. ISSN 0020-1669.
  6. ^ a b Fenske, Richard F.; DeKock, Roger L. (1970-05-01). "Electronic structure and bonding in manganese pentacarbonyl halides and hydride". Inorganic Chemistry. 9 (5): 1053–1060. doi:10.1021/ic50087a010. ISSN 0020-1669.
  7. ^ Liu, Xian-mei; Wang, Chao-yang; Qian-shu; Xie; Yaoming; King, R. Bruce; Schaefer, Henry F., III. Mononuclear and binuclear manganese carbonyl hydrides. Dalton Trans., 2009, 3774-3785, doi:10.1039/b822913a
  8. ^ Morris, Robert H. (2016-08-10). "Brønsted–Lowry Acid Strength of Metal Hydride and Dihydrogen Complexes". Chemical Reviews. 116 (15): 8588–8654. doi:10.1021/acs.chemrev.5b00695. hdl:1807/78047. ISSN 0009-2665. PMID 26963836.
  9. ^ Albertin, Gabriele; Antoniutti, Stefano; Bettiol, Massimo; Bordignon, Emilio; Busatto, Fabio (1997-11-01). "Synthesis, Characterization, and Reactivity of Cationic Molecular Hydrogen Complexes of Manganese(I)". Organometallics. 16 (23): 4959–4969. doi:10.1021/om970226j. ISSN 0276-7333.
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