Diimide

Diimide  | Ball and stick model of diazene ((E)-diazene)

E/trans-diazene

| Structural formula of diazene ((E)-diazene)

|

| Structural formula of diazene ((Z)-diazene)

Z/cis-diazene

| Ball and stick model of diazene ((Z)-diazene)

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Names
IUPAC name

Diazene

Other names

Diimide
Diimine
Dihydridodinitrogen
Azodihydrogen

Identifiers

CAS Number

* 3618-05-1 Y
* 15626-43-4 (E)-diazene Y
* 15626-42-3 (Z)-diazene Y

3D model (JSmol)

* Interactive image

ChEBI |

* CHEBI:30096 Y

ChemSpider |

* 10612167 Y

KEGG |

* C05360 Y

MeSH | Diazene

PubChem CID

* 123195

UNII |

* LM321PYV3Y Y

InChI

* InChI=1S/H2N2/c1-2/h1-2H Y

Key: RAABOESOVLLHRU-UHFFFAOYSA-N Y

* InChI=1/H2N2/c1-2/h1-2H

Key: RAABOESOVLLHRU-UHFFFAOYAG

SMILES

* N=N

Properties

Chemical formula

| H2N2
Molar mass | 30.030 g·mol−1
Appearance  | Yellow gas
Melting point |  −80 °C (−112 °F; 193 K)
Related compounds

Other anions

| diphosphene
dinitrogen difluoride

Other cations

| azo compounds

Related Binary azanes

* ammonia
* diazane
* triazane

Related compounds

* isodiazene
* triazene
* tetrazene

Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

N verify (what is YN ?)
Infobox references

Diimide, also called diazene or diimine, is a compound having the formula HN=NH. It exists as two geometric isomers, E (trans) and Z (cis). The term diazene is more common for organic derivatives of diimide. Thus, azobenzene is an example of an organic diazene.

## Contents

* 1 Synthesis
* 2 Applications to organic synthesis
* 2.1 Selectivity
* 3 Related
* 4 References

## Synthesis

A traditional route to diimide involves oxidation of hydrazine with hydrogen peroxide or air.[1] Alternatively the hydrolysis of diethyl azodicarboxylate or azodicarbonamide affords diimide:[2]

HO–C(=O)–N=N–C(=O)–OH → HN=NH + 2 CO
2[clarification needed]
NA2HA4+HA2OA2⟶NA2HA2+2HA2O

Nowadays, diimide is generated by thermal decomposition of 2,4,6‐triisopropylbenzenesulfonylhydrazide.[3]

Because of its instability, diimide is generated and used in-situ. A mixture of both the cis (Z-) and trans (E-) isomers is produced. Both isomers are unstable, and they undergo a slow interconversion. The trans isomer is more stable, but the cis isomer is the one that reacts with unsaturated substrates, therefore the equilibrium between them shifts towards the cis isomer due to Le Chatelier's principle. Some procedures call for the addition of carboxylic acids, which catalyse the cis–trans isomerization.[4] Diimide decomposes readily. Even at low temperatures, the more stable trans isomer rapidly undergoes various disproportionation reactions, primarily forming hydrazine and nitrogen gas:[5]

2 HN=NH → H
2N–NH
2 \+ N

Because of this competing decomposition reaction, reductions with diimide typically require a large excess of the precursor reagent.

## Applications to organic synthesis

Main article: Chemistry:Reductions with diimide

Diimide is occasionally useful as a reagent in organic synthesis.[4] It hydrogenates alkenes and alkynes with selective delivery of hydrogen from one face of the substrate resulting in the same stereoselectivty as metal-catalysed syn addition of H
2. The only coproduct released is nitrogen gas. Although the method is cumbersome, the use of diimide avoids the need for high pressures or hydrogen gas and metal catalysts, which can be expensive.[6] The hydrogenation mechanism involves a six-membered C

2 transition state:

### Selectivity

Diimide is advantageous because it selectively reduces alkenes and alkynes and is unreactive toward many functional groups that would interfere with normal catalytic hydrogenation. Thus, peroxides, alkyl halides, and thiols are tolerated by diimide, but these same groups would typically be degraded by metal catalysts. The reagent preferentially reduces alkynes and unhindered or strained alkenes[1] to the corresponding alkenes and alkanes.[4]

## Related

The dicationic form, H–N+
≡N+
–H (diazynediium, diprotonated dinitrogen), is calculated to have the strongest known chemical bond. This ion can be thought of as a doubly protonated nitrogen molecule. The relative bond strength order (RBSO) is 3.38.[7] F–N+
≡N+
–H (fluorodiazynediium ion) and F–N+
≡N+
–F (difluorodiazynediium ion) have slightly lower strength bonds.[7]

In the presence of strong bases, diimide deprotonates to form the pernitride anion, N−
=N−

## References

1. ↑ 1.0 1.1 Ohno, M.; Okamoto, M. (1973). "cis-Cyclododecene". Organic Syntheses. http://www.orgsyn.org/demo.aspx?prep=cv5p0281. ;  Collective Volume, 5, pp. 281
2. ↑ Wiberg, E.; Holleman, A. F. (2001). "1.2.7: Diimine, N2H2". Inorganic Chemistry. Elsevier. p. 628. ISBN 9780123526519. https://books.google.com/books?id=LxhQPdMRfVIC&pg=PA628.
3. ↑ Chamberlin, A. Richard; Sheppeck, James E.; Somoza, Alvaro (2008). "2,4,6-Triisopropylbenzenesulfonylhydrazide". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rt259.pub2. ISBN 978-0471936237.
4. ↑ 4.0 4.1 4.2 Pasto, D. J. (2001). "Diimide". Encyclopedia of Reagents for Organic Synthesis. John Wiley & Sons. doi:10.1002/047084289X.rd235. ISBN 0471936235.
5. ↑ Wiberg, Nils; Holleman, A. F.; Wiberg, Egon, eds (2001). Inorganic Chemistry. Academic Press. pp. 628–632. ISBN 978-0123526519.
6. ↑ Miller, C. E. (1965). "Hydrogenation with Diimide". Journal of Chemical Education 42 (5): 254–259. doi:10.1021/ed042p254. Bibcode: 1965JChEd..42..254M.
7. ↑ 7.0 7.1 Kalescky, Robert; Kraka, Elfi; Cremer, Dieter (12 September 2013). "Identification of the Strongest Bonds in Chemistry". The Journal of Physical Chemistry A 117 (36): 8981–8995. doi:10.1021/jp406200w. PMID 23927609. Bibcode: 2013JPCA..117.8981K.

* v
* t
* e

Binary compounds of hydrogen

Alkali metal (Group 1) hydrides|

* LiH
* NaH
* KH
* RbH
* CsH

Lithium hydride, LiH
ionic metal hydride

Beryllium hydride
Left (gas phase): BeH2
covalent metal hydride
Right: (BeH2)n (solid phase)
polymeric metal hydride

Borane and diborane
Left: BH3 (special conditions), covalent metalloid hydride
Right: B2H6 (standard conditions), dimeric metalloid hydride

Methane, CH4
covalent nonmetal hydride

Ammonia, NH3
covalent nonmetal hydride

Water, H2O
covalent nonmetal hydride

Hydrogen fluoride, HF
covalent nonmetal hydride

Alkaline (Group 2) earth hydrides|

| Monohydrides|

* BeH
* MgH
* CaH
* SrH
* BaH

|

Dihydrides|

* BeH2
* MgH2
* CaH2
* SrH2
* BaH2

|

Group 13 hydrides|

| Boranes|

* BH3
* B2H6
* B2H2
* B2H4
* B4H10
* B5H9
* B5H11
* B6H10
* B6H12
* B10H14
* B18H22

|

Alanes|

* AlH3
* Al2H6

|

Gallanes|

* GaH3
* Ga2H6

|

Indiganes|

* InH3
* In2H6

|

Thallanes|

* TlH3
* Tl2H6

|

Group 14 hydrides|

| Linear alkanes|

* CH4
* C2H6
* C3H8
* C4H10
* C5H12
* C6H14
* C7H16
* C8H18
* C9H20
* C10H22
* more...

|

Linear alkenes|

* C2H4
* C3H6
* C4H8
* C5H10
* C6H12
* C7H14
* C8H16
* C9H18
* C10H20
* more...

|

Linear alkynes|

* C2H2
* C3H4
* C4H6
* C5H8
* C6H10
* C7H12
* C8H14
* C9H16
* C10H18
* more...

|

Silanes|

* SiH4
* Si2H6
* Si3H8
* Si4H10
* Si5H12
* Si6H14
* Si7H16
* Si8H18
* Si9H20
* Si10H22
* more...

|

Silenes|

* Si2H4

|

Silynes|

* Si2H2
* SiH

|

Germanes|

* GeH4
* Ge2H6
* Ge3H8
* Ge4H10
* Ge5H12

|

Stannanes|

* SnH4
* Sn2H6

|

Plumbanes|

* PbH4

|

* CH
* CH2
* CH3
* C2H
* Cycloalkanes
* Cycloalkenes
* Annulenes
* Many more

Pnictogen (Group 15) hydrides|

| Azanes|

* NH3
* N2H4
* N3H5
* N4H6
* N5H7
* N6H8
* N7H9
* N8H10
* N9H11
* N10H12
* more...

|

Azenes|

* N2H2
* N3H3
* N4H4

|

Phosphanes|

* PH3
* P2H4
* P3H5
* P4H6
* P5H7
* P6H8
* P7H9
* P8H10
* P9H11
* P10H12
* more...

|

Phosphenes|

* P2H2
* P3H3
* P4H4

|

Arsanes|

* AsH3
* As2H4

|

Stibanes|

* SbH3

|

Bismuthanes|

* BiH3

|

* HN3
* NH
* radical

Hydrogen chalcogenides (Group 16 hydrides)|

| Polyoxidanes|

* H2O
* H2O2
* H2O3
* H2O4
* H2O5
* H2O6
* H2O7
* H2O8
* H2O9
* H2O10
* more...

|

Polysulfanes|

* H2S
* H2S2
* H2S3
* H2S4
* H2S5
* H2S6
* H2S7
* H2S8
* H2S9
* H2S10
* more...

|

Selanes|

* H2Se
* H2Se2

|

Tellanes|

* H2Te
* H2Te2

|

Polanes|

* PoH2

|

* HO
* HO2
* HO3
* H2O+–O–
* H2S=S
* (HS)2S+–S–
* HS
* HDO
* D2O
* T2O

Hydrogen halides (Group 17 hydrides)|

* HF
* HCl
* HBr
* HI
* HAt

Transition metal hydrides|

* ScH2
* YH2
* YH3
* TiH2
* ZrH2
* HfH2
* VH
* VH2
* NbH
* NbH2
* TaH
* CrH
* CrH2
* CrHx
* NiH
* PdHx (x < 1)
* FeH
* FeH2
* FeH5
* CuH
* ZnH2
* CdH2
* HgH2

Lanthanide hydrides|

* LaH2
* LaH3
* LaH10
* CeH2
* CeH3
* PrH2
* PrH3
* NdH2
* NdH3
* SmH2
* SmH3
* EuH2
* GdH2
* GdH3
* TbH2
* TbH3
* DyH2
* DyH3
* HoH2
* HoH3
* ErH2
* ErH3
* TmH2
* TmH3
* YbH2
* YbH2.5
* LuH2
* LuH3

Actinide hydrides|

* AcH2
* ThH2
* Th4H15
* PaH3
* UH3
* NpH2
* NpH3
* PuH2
* PuH3
* AmH2
* AmH3
* CmH2

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