CHM102A: General Chemistry
Inorganic Chemistry: Lecture 6B
Sabuj Kundu
sabuj@[Link]
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).
12
13
