Organometallic Chemistry Introduction to Organometallic Stability, Structure and bonding Organometallic Reactions Organometallic chemistry
By the end of this, you should be able to:
Understand the properties of organometallic compounds
Name organometallic compounds and Sketch their structures
Make an educated guess about stability and reactivity of a
given compound, based on electron counting rules
Describe the types of organometallic reactions
Use steric and electronic arguments to predict how changes
in reactants, metal or ligands affect the outcome of reactions Between organic and inorganic... Organic chemistry: more or less covalent C-X bonds fixed oxidation states
Knowledge of inorganic and coordination chemistry is useful to
understand geometries, electron counts and oxidation states of organometallic compounds
Organometallics are more covalent and often less symmetric than
coordination compounds.
Organometallic chemistry is concerned with all metals, in combination
with all "organic" elements.
We concentrate on the M side of the M-C bond, and on how to tune its reactivity Organometallic chemistry
Organic elements Main group metals Transition metals What is Organometallic chemistry
Organometallic chemistry is the study of chemical compounds
containing bonds between M-C or M-H.
Strictly speaking, the chemistry of compounds containing at
least one Metal-carbon bond Organometallic chemistry Since many compounds with such bonds are chemically similar, an alternative may be compounds containing metal-element bonds of a largely covalent character.
Thus, in practice many compounds are included that do not
actually contain metal-carbon bonds.
M-O Si-C B-C Some Examples of OMCs Some Examples of OMCs
Containing M-PR3 bond
Containing Si-C or B-C bonds
o The stability and reactivity of organometallic compounds are associated with the nature of the organic ligands and the metal to which they are attached.
o Physical states: Several of them exist as low melting solids, liquids or gases at ordinary temperatures.
o Solubility: The physical properties of organometallic compounds resemble with those of organic compounds at large.
For example, most of them are soluble in solvents of low polarity such as toluene, ethers etc. Classification of Organometallic Compounds
Based on type of metal-carbon bond
1. Main-group organometallics (Ionic): formed from most electropositive elements. M+R- highly electropositive metals low or negligible solubilities in non-polar solvents very reactive high melting pt. low volatility
The highly active main-group metals such as Na, Mg and Al
form highly air- and water-sensitive organometallic compounds.
For example, Al2(CH3)6 undergoes immediate and violent reaction
with water to liberate methane (CH4) gas, and it bursts immediately into flame on contact with air. Cont…
2. Covalent OMs: formed from less electropositive elements
Discrete molecule, volatile, and soluble in organic solvents
Most of them are slightly polar covalent:
Behave like organic compounds Low mpt. Volatile Soluble in non-polar solvents
1/28/22 Main-group organometallics
s and p orbitals. 8-e 8-e rule, usually. with a lot of exceptions
More electropositive and larger:
higher coordination numbers, 10-e regardless of the number of electrons.
“Early" groups and not very electropositive:
lower coordination numbers. 4-e Transition-metal organometallics s, p and d orbitals 18-e rule, sometimes 16-e other counts relatively rare
18-e 18-e 16-e
18-e rule: If the total number of electrons, which is equal to the
sum of d-electrons plus those contributed by the ligands are " 18 electrons = coordinatively saturated," < 18 electrons = coordinatively unsaturated" I. Compounds with one metal-carbon single bonds: Similar to transition metal coordination compounds (but here oxidation state of the metal is not included
•MeNa: methylsodium
•Me3Al: trimethylaluminum
•EtMePhAl: ethyl(methyl)phenylaluminium.
•Me2Hg: dimthylmercury
•[Ti(CH3)Cl3]: trichloro(methyl)titanium
•CH3MgBr: Methylmagnesium bromide
•Al(C2H5)2Br: Diethylaluminium bromide
II. Compounds with several metal-carbon single bonds from one ligand
oHapticity: the bonding of an organic ligand to a metal center via a contiguous series of carbon atoms.
The hapticity of a ligand is described by η ('eta' or hapto).
For example, η2 describes a ligand that coordinates through 2C atoms
oBridging ligands: are described with the µ notation. Atoms connected by a
bridging ligand are indicated by a right subscript, µn, where n≥2, though the bridging index 2 is not normally indicated.
Hapticity , ηx - “eta-x”: was originally developed to indicate how many carbons of a π-system were coordinated to a metal center. Used to describe the bonding mode of a ligand to a metal center ηx values for carbon ligands where the x value is odd usually indicate anionic carbon ligands e.g., η5-Cp, η1-CH3, η1-allyl or η3-allyl, η1-CH=CH2
The # of electrons donated (ionic method of electron counting) by the
ligand in the odd is usually equal to x + 1
Even ηx values usually indicate neutral carbon π-system ligands
The # of electrons donated by the ligand in the even (neutral) case is
usually just equal to x. Allyl ligands can bind in both a monohapto and trihapto form. The trihapto form can be expressed as a number of difference resonance forms as shown here for an unsubstituted allyl ligand: Hapto ligands and Sandwich compounds
(η5-C5H5)2Fe (η6-C6H6)2Cr
Sandwich
Bent Sandwich Half Sandwich
Ferrocene: Pathbreaking discovery of a sandwich compound
Kealy Pauson expected fulvalene
Ferrocene
G. Wilkinson E. O. Fischer R. B. Woodward 1973 Nobel Prize ‘sandwich compounds’ 1965 Nobel Prize ‘art of organic synthesis’ Ferrocene: Fuel additive, smoke suppressant and chiral catalyst precursor
Ferrocene powder Ferrocene crystals
Ferox Gas & Diesel Fuel Additive is a catalyst that is an eco-friendly fuel additive and horsepower booster. It allegedly increases mileage from between 10 and 20% while also significantly reducing harmful emissions. Naming/Ordering Common method of naming or ordering the listing of metal and ligands in a complex that most authors follow
1) In formulas with Cp (cyclopentadienyl) ligands, the Cp usually comes
first, followed by the metal center: Cp2TiH2
2) Other anionic multi-electron donating ligands are also often listed in
front of the metal. Cp2TiCl2
3) In formulas with hydride ligands, the hydride is sometimes listed first.
Rules # 1 & 2, however, take precedence over this rule: HRh(CO)(PPh3)2 Naming/Ordering
4) Bridging ligands are usually placed next to the metals in question, then followed by the other ligands (note that rules 1 & 2 take precedence): Co2(µ-CO)2(CO)6 , Rh2(µ-Cl)2(CO)4 , Cp2Fe2(µ-CO)2(CO)2
5) Anionic ligands are often listed before neutral ligands:
RhCl(PPh3)3, CpRuCl(PPh3), PtMe2bipy
In formulas Cp,Me,Anion, µ,Neutral
H, Me, Anion, µ,Neutral Sketch the structures of the following OMCs:
a) Bis(η6-benzene) chromium (0)
b) Di-µ-hydroxo octaaquadiiron (III) sulphate
c) Co2(µ-CO)2(CO)6
d) Ir2(µ-Cl)2(CO)4 [Ir(+1) = d8]
e) Cp2TiCl2 “18 Electron Rule” Carbonyl complexes and the 18-Electron rule The carbonyl ligand forms a huge number of complexes with metal ions, most commonly in low oxidation states, where it binds to the metal through its C-donor, as in the complexes below, where all the metal ions are zero-valent:
[Ni(CO)4] [Fe(CO)5] [Cr(CO)6]
Td TBP (D3h) Oh One might wonder why in the above complexes Ni(0) has four C≡O groups attached to it, Fe(0) five C≡O, and Cr(0) six C≡O. A very simple rule allows us to predict the numbers of donor groups attached to metal ions in organometallic complexes, called the eighteen electron rule. The latter rule states that the sum of the d-electrons possessed by the metal plus those donated by the ligands (2 per C≡O) must total eighteen:
[Ni(CO)4] [Fe(CO)5] [Cr(CO)6]
Ni(0) = d10 Fe(0) = d8 Cr(0) = d6
4 x CO = 8 5 x CO = 10 6 x CO = 12 18 e 18e 18e “18 Electron Rule”
Organic compounds, of course, follow the 8 electron rule: there can only be a maximum of 8 valence electrons around a carbon center
The vast majority of stable diamagnetic organometallic compounds have
18 or 16 valence electrons due to the presence of the five d orbitals which can hold 10 more electrons relative to C, O, N, etc.
Electron counting is the process of determining the number of valence
electrons about a metal center in a given transition metal complex
Complexes with 18 e- counts are referred to as saturated, because
there are no empty low-lying orbitals to which another incoming ligand can coordinate. Complexes with counts lower than 18e- are called unsaturated and can electronically bind additional ligands To determine the electron count for a metal complex
1) Note any overall charge on the metal complex
2) Determine the oxidation state of the transition metal
center
3) know the charges of the ligands bound to the metal center
4) know the number of electrons being donated from each
ligand to the metal center
5) Add up the electron counts for the metal center and ligands Electron counting Methods
Neutral (Covalent) Method of electron-counting
This considers everything to be neutral In this, Metal is taken as in zero oxidation state for counting purpose
Ionic (oxidation state) Method of electron-counting
The ionic method assigns formal charges to the metal and ligands In this, first arrive at the oxidation state of the metal by considering the number of anionic ligands present and overall charge of the complex
N.B: Focus on one counting method till you are confident
Easy way to remember ligand electron contribution Neutral method Electron contribution Neutral terminal : CO, PR3, NR3 2 Anionic terminal : X‐, H‐, R‐, Ar‐, R2N‐, R2P‐, RO‐ 1 Hapto ligands : η2‐C2R4, η2‐C2R2, η4‐C2R2,η1‐allyl, η3‐allyl, η4‐Cb, η5‐Cp, η6‐C6H6, η7‐C7H7, η8‐C8H8, η2‐C60, same as hapticity
Carbene M=C 2 Carbyne M≡C 3 Examples Metal carbonyls CN around the metal normally remains six or lesser. 17 electron species such as Mn(CO)5, Co(CO)4 dimerize to gain 18 electrons. V(CO)6 does not dimerize.
M-M single bond contributes 1 electron to count on each M
Metal-Metal bonding in Carbonyl complexes To check on the 18e rule, we look at one metal at a time: [Mn2(CO)10]
Mn(0) = d7 5 C≡O = 10 Mn-Mn = 1 18 e [Co2(CO)8] Co(0) = d9 3 CO’s = 6 2 bridge CO’s = 2 Co-Co bond = 1 18 e How bridging or terminal CO?? Infrared Spectroscopy‐Spectra of Metal Carbonyls Infrared Spectroscopy‐Spectra of Metal Carbonyls
The range in which the band appears decides bridging or terminal .
The number of bands is only related to the symmetry of the molecule Infrared Spectroscopy‐Spectra of Metal Carbonyls Neutral (Covalent) Method of electron-counting Charged ligands and the 18-Electron rule The formally charged ligands that are important in organometallic chemistry are mainly soft ligands such as Cl-, Br-, and I-, with CN- & H- are also also important. These mono-anionic ligands all contribute one electron for the 18-electron rule, as in the following examples: [Mn(CO)5Cl] [H2Fe(CO)4] [HCo(CO)4]
A substitution reaction is one in which an existing ligand
on a metal center is replaced by another ligand.
How this occurs depends on the electron count of the metal complex, the existing ligands on the metal, and their steric and electronic properties
The mechanism of this substitution will almost always depend on whether
the parent MLn complex is coordinatively saturated or not Ligand Substitutions Substitutions reactions occur by a combination of ligand addition and ligand dissociation reactions. Saturated Complex: Dissociative Pathway! Unsaturated Complex: Associative Pathway (usually)
Ligand Addition (association): If an incoming ligand coordinates
to a metal center that has one or more empty orbitals available Ligand Substitutions Ligand Dissociation: this is when a ligand coordinated to a metal dissociates. Depends on how strongly or weakly it is coordinated to the metal center and steric effects Ligand Substitutions
In unusual cases, Dissociative substitution can also occur in 16e- or
lower electron count systems complexes Ligand Substitutions
Steric Factors: Bulky (large) ligands occupy more space
around a metal center and can block incoming ligands trying to access vacant coordination sites on a metal
Due to steric hindrance, however, they are also more often to dissociate to relieve the steric strain
Consider, for example, the following equilibrium:
Note that there is virtually no Ni(PPh3)4 in solution: There is too much
steric hindrance with the bulky PPh3 ligands Associative Substitutions
These occur first by a ligand addition to the metal complex
followed by the dissociation of one of the original ligands. You typically need to have an unsaturated (17e- or lower) complex in order to propose an associative substitution mechanism Associative Substitutions
Consider, for example, the following Radical 17e- system
Electron rich metal complexes favor oxidative addition Oxidative Addition
An oxidative addition reaction is one in which (usually) a
neutral ligand adds to a metal center and in doing so oxidizes the metal, typically by 2e-. The transferring of the 2e- from the metal to the incoming ligand breaks a bond in that ligand forming two new anionic ligands. At least one of these new anionic ligands ends up bonded to the metal center Oxidative Addition
An oxidative addition reaction is one in which (usually) a
neutral ligand adds to a metal center and in doing so oxidizes the metal, typically by 2e-. The transferring of the 2e- from the metal to the incoming ligand breaks a bond in that ligand forming two new anionic ligands. At least one of these new anionic ligands ends up bonded to the metal center Oxidative Addition
Because oxidative addition involves oxidation (removal of
electrons) of the metal center, the more electron-rich the metal is the easier the oxidative addition to the metal center will be. d0 metals can NOT do oxidative additions!! So always count electron of the starting and final metal complexes to check out the overall electron-count of metal oxidation state and d-electron count Once you get used to looking at organometallic rxns you will be able to identify common oxidative additions quite quickly. H2, R-X, and H-SiR3 are three of the most common substrates that perform oxidative addition reactions in catalytic cycles Requirements for the Metal Complex (1) Metal centre must be d2 or greater (2) Metal centre must be coordinatively unsaturated, have appropriate vacant orbitals Reductive Elimination The reverse of an oxidative addition Electron deficent metal complexes favor reductive Elimination It is a reaction in which two cisoidal anionic ligands on a metal center couple together
Since reductive elimination involves pushing electrons back
onto the metal center from two anionic ligands that are usually more electronegative than the metal center, it is best if the metal center is electron deficient.
This can be accomplished
by having electron-withdrawing ligands (e.g., CO) cationic charge (s), and/or coordinative unsaturation (sub-18e- counts) Migratory Insertion
is when a cisoidal anionic and neutral ligand on a metal complex
couple together to generate a new coordinated anionic ligand
General Features: 1) No change in formal oxidation state
2) The two groups that react must be cisoidal to one another
3) Vacant coordination site is generated by the migratory insertion.
• Therefore, a vacant site is required for the back elimination reaction a trapping ligand is often needed to coordinate to • the empty site formed from a migratory insertion in order to stop the back elimination reaction 4) Migratory insertions are favored on more electron-deficient metal centers. Migration vs. Insertion α, β, δ hdride elimination
Elimination reactions are just the reverse of migratory insertion reactions
• β-hydride elimination is the reverse of 1,2 insertion • An alkene and a hydride usually react via a migration of the hydride to the coordinated alkene ligand forming an alkene α, β hdride elimination
α –hydride elimination yields carbene or carbyne
Excercises Identify the following reactions by their type (migratory insertion, elimination, β-hydride elimination, oxidative addition, reductive elimination, ligand addition, ligand dissociation, ligand coordination change, etc.). Note that in some cases you will have to use more than one description for a reaction that has several steps. Note also that the order may be important! Given the following Redox organometallic reactions. A B
Identify the type of reaction from A to B and B to A. ??
Identify the most stable complexes, explain your choice. ??
