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IC - Lecture 6B

The document discusses inorganic chemistry topics such as bridging ligands, metal carbonyls, and metal alkene complexes. It describes how bridging ligands donate electrons to metals and how infrared spectroscopy can provide information about metal carbonyl bonding. It also explains the sigma and pi bonding between metals and alkene ligands.

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19 views

IC - Lecture 6B

The document discusses inorganic chemistry topics such as bridging ligands, metal carbonyls, and metal alkene complexes. It describes how bridging ligands donate electrons to metals and how infrared spectroscopy can provide information about metal carbonyl bonding. It also explains the sigma and pi bonding between metals and alkene ligands.

Uploaded by

Dusu
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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CHM102A: General Chemistry

Inorganic Chemistry: Lecture 6B

Sabuj Kundu
[email protected]
1
Bridging Ligands: Electron Counts
❑A bridging carbonyl is like a ketone from the point of view of
electron counting; it is a 1e donor to each metal. (This is true for
both models because users of the ionic model regard CO as a neutral
ligand even when bridging.)

2
Metal Carbonyls
Infrared (IR) Spectroscopy of Metal Carbonyls
❑IR spectra provides information about the stretching frequency of
a bond. Stronger bonds will have the higher stretching frequency.

❑Look for electron density at the metal center: (CO) is directly


corelated to this. If metal is more electron rich: more back bonding
to the * orbital of CO: hence (CO) will decrease.
❑How you can control the electron density on metal?

Free CO; (CO) = 2143 cm-1

4
Bridging vs Terminal Carbonyls
❑ Bridging CO groups can be regarded as having a double bond C=O
group, as compared to a terminal C≡O, which is more like a triple
bond:
terminal carbonyl bridging carbonyl
(~ 1850-2125 cm-1) (~1700-1860 cm-1)

❑ Based on the CO stretching frequencies we can predict presence of a


bridging or terminal CO groups.
Metal η2-Alkene (olefin) complexes
❑Among the most distinctive aspects of organometallic
chemistry is the ability of a wide variety of ligands
containing π-electron systems to form π-bonds to metals.

❑η2-Alkene (olefin) complexes now exist of every


transition metal and constitute one of the most important
classes of coordination compounds.

6
Metal η2-Alkene (olefin) complexes
❑In 1827, the Danish chemist Zeise obtained a new compound he
took to be KCl·PtCl2·EtOH from the reaction of K2PtCl4 with EtOH.

❑Only in the 1950s was it established that Zeise’s salt, is really


K[PtCl3(C2H4)]·H2O, containing a coordinated ethylene, formed by
dehydration of the ethanol, and a water of crystallization.

7
Bonding in metal-alkene complexes

8
Bonding in metal-alkene complexes

❑This involves donation of the C=C π electrons to an empty dσ


orbital on the metal, so this electron pair is now delocalized over
three centers: M, C, and C.

❑This is accompanied by back donation from a metal dπ orbital into


the ligand C=C π∗ level (occupied orbitals shaded).
9
Bonding in metal-alkene complexes
❑The C=C bond of the alkene lengthens on binding. The M−alkene σ
bond depletes the C=C π bond by partial transfer of these electrons to
the metal and so slightly weakens and, therefore, lengthens it.

❑The major factor in lengthening the C=C bond, however, is the


strength of back donation from the metal.

❑By filling the π∗ orbital of the C=C group, this back donation can
sharply lower the C−C bond order of the coordinated alkene.

❑For Zeise’s salt, M−L σ bonding predominates because the Pt(II) is


weakly π basic, and the ligand (C−C: 1.375 ˚A) more nearly
resembles the free alkene (1.337 ˚A).

10
Bonding in metal-alkene complexes
❑For Zeise’s salt, M−L σ bonding predominates because the Pt(II) is
weakly π basic, and the ligand (C−C: 1.375 ˚A) more nearly
resembles the free alkene (1.337 ˚A).

❑Pt(0), in contrast, is much more strongly π basic, and in


Pt(PPh3)2(C2H4), the C−C distance becomes much longer (1.43 ˚A).

❑In such a case the metal alkene system approaches the


metalacyclopropane extreme, as contrasted with the Dewar–Chatt
model, both are considered η2 structures.

11
Bonding in metal-alkene complexes

❑In the metalacyclopropane extreme (i.e., cyclopropane with M


replacing one CH2 group), the substituents on carbon are strongly
folded back away from the metal as the carbons rehybridize from
sp2 to something more closely approaching sp3.

❑ The presence of electron-withdrawing groups on the alkene also


encourages back donation and makes the alkene bind more strongly
to the metal; for example, Pt(PPh3)2(C2CN4) has an even longer C−C
distance (1.49 ˚A) than the C2H4 complex (1.43 ˚A).
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