HYDRIDES AND DIHYDROGEN

Group 2 Members:
172392 Shalini Manian
173111 Faziatul Amira Rosli
174429 Sylviana Awing Lawai
173509 Azlin Maslyana Abu Bakar
175176 Nur Syuhada Ahmad Taufik
HYDRIDES
Introduction
Hydrides
• The term hydride is commonly named after binary compounds that
hydrogen forms with other elements of the periodic table.

• Hydrides are classified into three major groups which are

covalent,ionic and metallic hydrides.

• Covalent hydrides- hydrogen atom with one or more non-metals form

compounds (eg formation of hydrochloric acid).

• Ionic hydrides - These compounds form between hydrogen and the

most active metals, especially with the alkali and alkaline-earth
metals of group one and two elements.
• Eg : Alkali Metal Hydrides
• when an alkali metal reacts with hydrogen gas under heat, an ionic
hydride is produced. Alkali metal hydrides also react with water to
produce hydrogen gas and a hydroxide salt:
• MH (s) +H2O (l) →MOH (aq) +H2(g)

• Metallic Hydrides – interaction of hydrogen bonds with transition

metals.

• In organometallic chemistry, metal hydrides occupy an important

place in transition metal as the M−H bonds.

• The first transition metal hydride compound was reported by W.

Heiber in 1931 when he synthesized Fe(CO)4H2
DIHYDROGEN
Introduction
Dihydrogen
• Dihydrogen complexes are coordination complex containing
intact H2 as a ligand. In fact, many dihydrogen complexes exist
in equilibria with their dihydride form:
 SPECIAL
CHARACTERISTICS
Special characteristics
Hydride
• Only some hydrides are connected with hydrogen bonding.

• In hydrides, hydrogen is bonded with a highly electronegative atom so

their properties are more distinguished. Such that in groups 14-17
hydrides, the values of ammonia (NH3), water (H2O), and hydrogen
fluoride (HF) break the increasing boiling point trend.

• Supposedly, as the molecular mass increases, the boiling points

increase as well. Due to the hydrogen bonds of the three following
hydrides, they distinctly have high boiling points instead of the initial
assumption of having the lowest boiling points. What occur in these
hydrogen bonds are strong dipole-dipole attractions because of the
high ionic character of the compounds.
Special characteristics
Dihydrogen complex
• The simplest variant of a σ−complex contains a dihydrogen ligand. The
first dihydrogen complex was isolated by Kubas, after which many
new ones were reported.
• if the metal center is electron rich, then further back donation to the
σ* orbital of the metal bound H−H moiety may occur resulting in a
complete cleavage of the H−H bond.

• Quite expectedly, the dihydrogen moiety bound to a metal in a

σ−complex is found to be more acidic (pKa = 0 − 20) when compared
to the free dihydrogen molecule (pKa = 35).
BONDING MODE
IN HYDRIDE
COMPLEXES
General information

• Contains metal-hydrogen bond

• Consists of two types of bonding, which are terminal bonding

and bridging bonding (the most common bonding mode)

Bridging bonding
• Is the most common bonding mode
• Does not contain the M-H-M angle
• Has the three-centre two-electron bonding situation
• M-H sigma bond will be the electron donor itself
• Thus, enabling the hydride to bind end-to-end to one metal
Example of bridging bonding

Resonance forms of bridging hydride

Further example of bridging bonding of hydride
BONDING MODE
IN DIHYDROGEN
COMPLEXES
 Dihydrogen bonding mode
• Coordination complexes containing intact H2 as a ligand.
• The prototypical complex is W(CO)3(PCy3)2(H2).
• Most examples are cationic transition metals complexes with octahedral
geometry.
• Metal is more electropositive than hydrogen.
• The complex is an arrested intermediate in the oxidative addition of
dihydrogen.
• Oxidative addition is an organometallic chemistry process that
increases both the oxidation state and coordination number of a
metal centre.
• Mildly backbonding metals may bind dihydrogen “side on.”
• The bonding of dihydrogen involves a combination of π and σ bonding.
• The σ donation comes from the bonding dihydrogen orbital.
• The π backbonding arises from donation of metal d orbital electron
density into the dihydrogen antibonding orbital.
• Dihydrogen complexes can “tautomerize” to (H)2 isomers through
oxidative addition of the H–H bond to the metal.
• Oxidative addition of H2 is important for electron-rich, π-basic metal
centers. Groups 6-9 metals are more favourable for oxidative addition.
• M–H bond can participate in hydrogen bonding with an
acidic X–H bond, where X is a heteroatom.
• This kind of bonding, called dihydrogen bonding.
• σM–H→σ*X–H orbital interaction.

Dihydrogen bonding in metal hydrides: a sort of

"interrupted protonation" of M–H.
SYNTHESIS OF
HYDRIDES
COMPLEXES
 From
hydride (H-)
donor
Oxidative
Protonation
addition

Synthesis of
Hydride
Complexes
1) Protonation
 Metal center has to be basic and electron rich
1)

2)
More synthesis by protonation:

3)

4)

5)
2) From hydride (H-) donor
 Main group hydride is reacted with metal halide
3) By oxidative addition
 Oxidative-addition of hydrogen to a metal complex
SYNTHESIS OF
DIHYDROGEN
COMPLEXES
SYNTHESIS OF DIHYDROGEN COMPLEXES
• Involve 2 preparation methods of direct reactions with H2 gas
• More easily prepared by exposing a precursor compound to hydrogen gas

A labile ligand contain an easily displaced

agostic interaction Refer to C-H bond on ligand
that undergoes an
interaction with metal
complex

1) The addition of H2 to an unsaturated metal center, H2 will displace weakly

bound ligands
LnMX + H2 → [LnM(H2)]+ + X−

2) Protonation of metal hydrides

LnM−H + H+ → [LnM(H2)]+
SYNTHESIS OF DIHYDROGEN COMPLEXES
Example : Nickel dihydrogen complexes
Mo dihydrogen complexes
Transition metals

Group 6 – Group 9
REFERENCES
• http://www.mpilkington.com/Lecture_19.pdf
• http://www.chem.tamu.edu/rgroup/marcetta/chem462/lectures/Hyd
rogen%20and%20Catalysis.pdf
• http://web.mit.edu/5.03/www/notes/hydride_dihydrogen.pdf
• http://classes.uleth.ca/201103/chem4000b/Hydride%20and%20H2%
20Ligands.pdf
• https://chem.libretexts.org/Core/Inorganic_Chemistry/Descriptive_C
hemistry/Main_Group_Reactions/Compounds/Hydrides
• http://www.ilpi.com/organomet/hydride.html
• http://www.ilpi.com/organomet/dihydrogen.html