Pentacarbonylhydridomanganese

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Pentacarbonylhydridomanganese
Pentacarbonylhydridomanganese HMn(CO)5-2D.png
Pentacarbonylhydridomanganese
Pentacarbonylhydridomanganese-3D-balls.png
Names
Other names
Hydrogen pentacarbonylmanganate(−I) (7CI); Manganese, pentacarbonylhydro- (8CI); Hydridomanganese pentacarbonyl; Hydridopentacarbonylmanganese; Manganese pentacarbonyl hydride; Pentacarbonylhydromanganese; Pentacarbonylmanganese hydride
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/5CO.Mn.H/c5*1-2;;
    Key: SKOPWNLHPUYPLV-UHFFFAOYSA-N
  • O=C=[MnH](=C=O)(=C=O)(=C=O)=C=O
Properties
HMn(CO)5
Molar mass 195.99799 g/mol
AppearanceAt 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 [77 °F], 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.

Contents

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 [Mn(CO)
5
]
can be isolated as crystalline PPN+
(μ-nitrido—bis-(triphenylphosphorus)) salt, which is smoothly protonated by CF
3
SO
3
H
. [3]

PPN[Mn(CO)
5
] + CF
3
SO
3
H
→ HMn(CO)5 + PPN+
CF
3
SO
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

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