Organometallics

― Introduction ❑ The 18-electron Rule or Effective atomic number (EAN)

― Stability ➢ The rule states that: “thermodynamically stable transition metal
― Structure and applications of organometallic compounds are formed when the sum of the metal d
→ Metal carbonyls electrons and the electrons conventionally considered as being supplied by
→ Ferrocene the surrounding ligands equals to 18”
➢ to decide whether a given d-block transition metal
organometallic complex is likely to be stable.
 Organic formulas & their stability: the Octet rule  The 18e rule: applies to low-valent transition metal
 2nd row elements (B, C, N, O, F): 4 valence orbitals complexes following a similar line of reasoning.
(2s, 2px, 2py, 2pz) → can accommodate 8 electrons
 Metal → one s, three p, five d orbitals . 18 electrons
# CH5 → requires 5-valent carbon & not stable. to fill all nine orbitals  18-electron rule
# CH4 → Stable compound & has noble gas octet → some come from metal, the rest from the ligands

❑ Counting electrons for metal complex

I. note any overall charge on the metal complex
II. know the charges of the ligands bound to the metal center (ionic ligand method)
III. know the number of electrons being donated to the metal center from each ligand (ionic ligand method)
 Organometallics

― Introduction ➢ Ionic Model: number of e = no. metal electrons (dn) + no. ligand electrons
― Stability
― Structure and applications of number of valence electrons for a metal at donate 2 electrons
→ Metal carbonyls the oxidation state present in the complex
→ Ferrocene  with 18 electrons: Saturated, whereas lower than
18 electrons: Unsaturated
❑ Electron Counting
I. Determine the oxidation state of the metal.
→ Balance the ligand charges with an equal opposite
charge on the metal  metal's formal oxidation state.
→ Ligand charge: create an ionic model by assigning each M-L
electron pair to the more electronegative atom (L). This
should result in stable ligand species or known as reaction
intermediates in solution.
II. d electron count
→ subtract the metal's oxidation state from its group no.
❖ Determine the electron count of the complex
→ by adding the # of electrons donated by each ligand to
the metal's d electron count.
 Organometallics

― Introduction I. no overall charge on the complex Re(+1) : d6

― Stability II. one anionic ligand (CH3− group) 2 PR3 : 4e-
― Structure and applications of III. Re metal must have a +1 charge 2 CO :4e-
→ Metal carbonyls  +1 oxidation state. We denote CH3− :2e-
→ Ferrocene this in two different ways: CH2=CH2 :2e-
Re(+1), Re(I), or ReI. Total: 18e-
 Organometallics

― Introduction ❑ Metal-Carbonyls
― Stability  Formation of σ-bond: empty hybrid
― Structure and applications of orbital of metal atom overlaps with the
→ Metal carbonyls filled hybrid orbital of carbon atom of CO
→ Ferrocene molecule formation of a M←CO σ-bond.
 Formation of π-bond by back donation:
overlapping of filled dπ orbitals or hybrid
✓ Powerful π-acceptor ligand
dpπ orbitals of metal atom with
✓ Excellent ligand for stabilizing low-valent metal centers
antibonding pi orbitals on CO molecule.

Terminal mode

μ2-bridging μ3-bridging
➢ going from a terminal bonding mode to μ2-
& μ3-bridging mode  relatively drop in
the CO stretching frequency seen in the IR.
 Organometallics
For neutral
― Introduction
metal complexes
― Stability
― Structure and applications of
→ Metal carbonyls ❑ Ligand Donation Effects
→ Ferrocene
◙ ability of the ligands to donate electron density to the metal center has
considerable effect on the absolute amount of electron density on that metal.
◙ It effects the νCO IR stretching frequencies in metal carbonyl complexes.
 2 trans π-backbonding ligands will compete for the same d-orbital
electron density, weakening each others net M-L π-backbonding.
 σ-donating trans ligand can increase the M-CO bond strength (more
M=C=O character) by allowing unimpeded M→CO π-backbonding.
 Besides, traditional σ-donor/π-acceptor to one/more metal centers,
CO can act as a π-donor to additional metals.
 For more electron deficient metal complexes where metal centers
are not favoring π-backbond to the carbonyl, but can accept
electron density to the empty orbitals from the carbonyl π-system.
σ/π Bridging CO  The CO ligand here can act as a 4 or 6 electron donor!
 Organometallics

― Introduction ❑ Structure of Ni(CO)4

― Stability
― Structure and applications of
→ Metal carbonyls
→ Ferrocene

tetrahedral
➢ Determination of geometries of Carbonyls:
→ calculating number of IR active bands
➢ Determination of Bond orders:
→ IR absorption frequency of ligated CO  its Bond Order (BO)
Trigonal bipyramidal → Higher the IR absorption band  Stretching vibration of ligated CO with a
higher BO occur at a higher frequency
→ the absorption frequency for free CO ≈ 2250 cm─1 while for ligated CO ≈ 2220-1700 cm─1
→ ligated CO has lower BO, due to the transfer of metal dπ electrons into the π* orbitals of
ligated CO.
 Organometallics

― Introduction Metal Carbonyl [V(CO)6]─ [Cr(CO)6]─ [Mn(CO)6]+

― Stability
Charge on Metal -1 0 +1
― Structure and applications of
Absorption frequency for CO (cm ─1) 1860 1980 2090
→ Metal carbonyls
→ Ferrocene
# The positive charge on [Mn(CO)6]+ resists the flow of metal dπ electrons into the
π* orbitals of CO  the BO of CO increases  the absorption band of ligated
CO occurs at higher frequency (= 2090 cm─1)

➢ Difference between terminal

and bridging carbonyl groups
➢ Studying the reaction rates:
→ following the rates of
disappearance of the intensity of
CO absorption bands in the IR
spectra can be used to study the
rates of substitution reaction of
metal carbonyls
 Organometallics

― Introduction ❑ Applications
― Stability  Metal carbonyls are useful in organic synthesis as catalysts
― Structure and applications of → Dicobalt octacarbonyl (Co2(CO)8) acts as homogeneous catalyst
→ Metal carbonyls o for hydroformylation: H2 + CO + CH3CH=CH2 → CH3CH2CH2CHO
→ Ferrocene
o for hydrosilylation of olefins

 In the Mond process, nickel carbonyl is used to produce pure nickel

 Fe(CO)5 is used for the preparation of inductors, pigments, as dietary

supplements, in the production of radar-absorbing materials in the
stealth technology, and in thermal spraying.
 Metal carbonyls are used in a number of industrially important carbonylation reactions.
o In the oxo process: o Several other Metal-Carbonyl complexes have been employed
in the hydrocarboxylation and hydrogenation reactions.
 Organometallics

― Introduction ➢ Fe in ferrocene is in +2 oxidation state (according to

― Stability Mössbauer spectroscopy)
― Structure and applications of
➢ Each cyclopentadienyl (Cp) ring has a single negative charge.
→ Metal carbonyls ➢ Ferrocene: Iron(II) bis(cyclopentadienide) Fe2+[C5H5- ]2.
→ Ferrocene ➢ π-electrons on each ring = six  aromatic w. r. t. Hückel's rule.
➢ 12 π-electrons are shared with the metal via covalent bonding.
➢ Fe2+ has six d-electrons, the complex attains an 18-electron configuration, which accounts for its stability.
➢ The sandwich structural model of the Ferrocene molecule is denoted as Fe(η5-C5H5)2.
➢ Crystallography reveals that the cyclopentadienide rings are in staggered conformation.
➢ Hybridization: d2sp3
➢ Magnetic Nature: Diamagnetic ✓ Pharmaceutical: Ferrocene derivatives have been
investigated as drugs
✓ Fuel additives: Ferrocene and ✓ e.g. one drug has entered clinic trials, Ferroquine (7-
Applications its derivatives are used as chloro-N-(2-((dimethylamino)methyl)ferrocenyl)quinolin-
of antiknock agents in the fuel for 4-amine) as an antimalarial drug.
Ferrocene petrol engines. They are safer
✓ Ferrocene-containing polymer-based drug delivery
than previously TEL systems have been investigated.