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Metal Carbonyls II

D. Jim Livingston
Asst. Professor of Chemistry
St. John’s College.
Infrared spectroscopy
• Infrared spectroscopy (IR spectroscopy or vibrational
spectroscopy) involves the interaction of infrared radiation
with matter.
• This can be analyzed in three ways by measuring absorption,
emission and reflection.
• mostly based on absorption spectroscopy to identify solid,
liquid, or gas samples.
• IR Spectroscopy measures the vibrations of atoms -
determine the functional groups
• An IR spectrum can be visualized in a graph of infrared light
absorbance (or transmittance) on the vertical axis (x) vs.
frequency or wavelength on the horizontal axis (y).
• Units - reciprocal centimeters (wave numbers),cm−1.
• Generally, stronger bonds will vibrate at a high stretching
frequency (wavenumber)
Vibrations of molecules
• A common
laboratory
FT - IR Instrument instrument -
Fourier transform
infrared (FTIR)
spectrometer.
An IR spectrum
Effect of electron density on metal

If Electron density on metal increases


i.e., -ve charge on metal increases or M in low oxidation state

Π- back bonding
increases

M-C bond order


increases
C-O bond order
decreases
Check Your understanding
• Arrange the following complex in the decreasing order of carbonyl
stretching frequency.
• Fe(CO)3]4-, Fe(CO)5, V(CO)6]-, Mn(CO)6]+

• Arrange the following in the increasing order of M-C bond length.


• [Ni(CO)4], [Co(CO)4]- and [Fe(CO)4]2-

Answers
Mn(CO)6]+ > Fe(CO)5 >V(CO)6]- > Fe(CO)3]4-

[Fe(CO)4]2- < [Co(CO)4]- < [Ni(CO)4]


Nickel tetracarbonyl
Tetrahedral
Bond length: 1.5 A0
Diamgnetic
iron pentacarbonyl.
Trigonal
bipyramidal

axial
1.80 Å

Equatorial
1.84 Å
diamagnetic
hexacarbonylchromium
octahedral

1.92 Å

diamagnetic
Mn2(CO)10, Dimanganese decacarbonyl

Square pyramidal

Mn-Mn bond length


2.79 Å
Co2(CO)8, Dicobalt octacarbonyl
exist in two
isomeric forms
Fe2 (CO) 9, Diiron nonacarbonyl

Fe-Fe bond 2.46 Å


Fe3(CO)12, Triiron dodecacarbonyl

3-membered ring structure


Terminal CO for one Fe Fe-Fe 2.8 Å
Terminal CO for two Fe
Bridging CO overall
References
1. Adv. Inorganic chemistry Vol II, SatyaPrakash, G.D. Tuli.
2. Inorganic Chemistry, Shriver and Atkins
3. Inorganic Chemistry: Principles of Structure and Reactivity, James
E. Huheey, Ellen A. Keiter, Richard L. Keiter, Okhil K. Medhi
4. Concise Co-ordination Chemistry, Ramalingam and Gopalan.
5. http://www.chem.iitb.ac.in/~rmv/ch102/ic6.pdf

-Thank You