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Metal Carbonyls

This document discusses metal carbonyls and infrared spectroscopy. It provides details on how infrared spectroscopy can be used to identify functional groups and determine bond lengths and orders by analyzing absorption, emission, and reflection patterns in infrared spectra. Specifically, it examines the vibrations of metal carbonyl complexes and how factors like electron density on the metal impact bonding. Examples of common metal carbonyl complexes are given like nickel tetracarbonyl and their structures. References for further reading on metal carbonyls and inorganic chemistry are also listed.

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Jim Livingston
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4K views17 pages

Metal Carbonyls

This document discusses metal carbonyls and infrared spectroscopy. It provides details on how infrared spectroscopy can be used to identify functional groups and determine bond lengths and orders by analyzing absorption, emission, and reflection patterns in infrared spectra. Specifically, it examines the vibrations of metal carbonyl complexes and how factors like electron density on the metal impact bonding. Examples of common metal carbonyl complexes are given like nickel tetracarbonyl and their structures. References for further reading on metal carbonyls and inorganic chemistry are also listed.

Uploaded by

Jim Livingston
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PPT, PDF, TXT or read online on Scribd
  • Introduction to Metal Carbonyls II: Presents an overview of the document and introduces the speaker and institution.
  • Infrared Spectroscopy Overview: Discusses the principles of infrared spectroscopy focusing on the interaction of infrared radiation with matter and its applications.
  • Molecular Vibrations: Visual representation of molecular vibrations explaining the concept related to spectroscopy.
  • FT-IR Instrumentation: Details equipment used in Fourier transform infrared spectroscopy and its laboratory applications.
  • Interpreting IR Spectrum: Shows and explains the characteristics of an infrared spectrum with emphasis on vibration peaks.
  • Infrared Spectra Reports: Explains different types of CO groups found in organometallic compounds using infrared spectra.
  • Effects of Electron Density: Analyzes how electron density affects metals, including changes in bond order and evidence from IR.
  • Check Your Understanding: Provides exercise questions to test understanding of carbonyl stretching frequency and bond lengths.
  • Nickel Tetracarbonyl: Describes the structure and properties of nickel tetracarbonyl, focusing on its tetrahedral shape and bond lengths.
  • Iron Pentacarbonyl: Explores the structure and magnetic characteristics of iron pentacarbonyl, including its trigonal bipyramidal shape.
  • Hexacarbonylchromium: Illustrates the octahedral configuration of hexacarbonylchromium and its bond length measurements.
  • Dimanganese Decacarbonyl: Analyzes the square pyramidal structure of dimanganese decacarbonyl with its unique bond features.
  • Dicobalt Octacarbonyl: Discusses the isomeric forms and catalytic properties of dicobalt octacarbonyl.
  • Diiron Nonacarbonyl: Describes the bonding and structural details of diiron nonacarbonyl, highlighting its carbonyl groups.
  • Triiron Dodecacarbonyl: Explains the tri-membered ring structure of triiron dodecacarbonyl and its bridging carbonyl features.
  • References: Lists literature and resources referenced throughout the presentation on metal carbonyls.

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. [Link]

-Thank You

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