CHM 4301

Advanced inorganic
Bonding in organometallic
compound:
Alkyl group
INTRODUCTION
 What is alkyl?
O alkyl substituent is an alkane missing one hydrogen
O The general formula for an alkyl is CnH2n+1
O The designations given are n-(normal),sec-(secondary),iso-
and tert(tertiary).
 What is organometallic compounds?

O Organometallic compounds: containing direct

metal-carbon bonds.
O Either s or p bonds can occur

Main group:

(AlMe3)2
 Why metal alkyl?
O Metal alkyls feature a metal-carbon σ bond and are usually
actor ligands
O aim will be to understand the general dependence of the
behavior of alkyl ligands on the metal center and the ligand’s
substituents
O alkyl ligands are central to organometallic chemistry

CH3
M
1.1 BONDING AND BRIDGING
1.1.1 Bonding – Group 14 Elements

O Most closest noncarbon analogue of metal alkyl

: Metal silyl M-SiR3
(R = alkyl, aryl, or OH)
O Trimethylsilyl transition metal complexes - one of
the stable rare complexes due to :
 𝛽 elimination involving Me3Si, inhibited by
relative instability of Si=C double bonds
 Less sterically congested than CMe3 group
 M-SiR3 bonds are strong
 1.2 Bonding
 For simple metal alkyls, the M-R bond distance is typically 190 to
220 pm. This is approximately the sum of the covalent radii of
carbon and metal, rC = 77 pm and rM ~120 pm.

 Realize that the first row transition metals are smaller, so any M-
X bond distance will usually be smaller by 10-20 pm or so

 Alkyl group are often found as ligands in d-metal organometallic

chemistry and their bonding present no new features

 Best considered as a simple convalent σ interaction between the

metal atom and the carbon atom of the organic fragment.
 1.1.2 Bridging alkyl and related ligand.
O Alkyls can also bridging ligands.
O For the main group element Al, this seem to happen by a
2e, three-center bond involving only the metals and
carbon [eg.,Me4Al2(μ-Me)2].
O This well known from aluminum-alkyl chemistry.
 For example, consider the condensed phase structure of these Al-alkyls
(see Oliver et. al. Organometallics 1982, 1, 1307):

 For Al2Me6, sharp resonances for bridging and terminal Me groups at -

75 degrees C in the 1H NMR, but these coalesce and are one average
signal at room temperature. This indicates a very low barrier to
interconversion of the two groups. Interestingly, the dimer-monomer
equilibrium contains only 0.0047 % monomer at 20 C.
O Bridging alkyls are also known for other metals such as lanthanum and
zirconium (Waymouth, Santarsiero, Grubbs J. Am. Chem. Soc. 1984, 106,
4050-4051):

 In this structure, the bridging Me group is nearly planar (C is only 8 pm out of

the plane defined by the three methyl hydrogens vs. 30 pm for a typical sp3
carbon).
 The Me bridge is slightly asymmetric (Zr1-C = 259.9(7) and Zr2-C = 245.6(7)
pm ) and the Zr-C-Zr angle is 147.8(3) degrees. This non-linearity was ascribed
to better orbital overlap on the basis of MO calculations.
 The JCH = 136 Hz, indicating a fair amount of sp2 character.
O On the other hand, the transition metal tend to preferny an agnostic C-
H bond.

O A number of remarkable bridges have also been found that involve an

essentially planar methyl with the two dᴼ metal coordinated each side
of the plane.
 1.2 SPECIAL
CHARACTERISTIC
1.2 SPECIAL CHARACTERISTICS
1.2.1 General properties
1. Metal’s electronegativity
- reactivity of alkly ligand depends on
electronegativity of metal center
- if electronegativity of metal increases, the its
reactivity of alkyl ligand decreases
2. Hybridization
- reactivity of alkly ligand depends on hybridization
- as the hybrid orbital s character increase, then the
reactivity will be decrease
- sp-Hybridized ligands are the least nucleophilic, followed
by sp2 and sp3 ligands respectively
 18-Electron Rule
O 18e rule is a way to help us decide whether
a given d-block transition metal
organometallic complex is likely to be stable
O 18e rule applies to many low-valent trasition
metal complexes
O The 18e rule supposed to fill all nine orbitals
(1 s orbital, 3 p orbitals and 5 d orbitals)
1.2.2 Properties of stable alkyl complexes
- Must be resistant to β-hydride elimination.
- Stable alkyl complexes must violate at least one of these
conditions:
1.) The β-carbon must support a hydrogen.

2. ) The M–C and C–H bonds must be able to achieve

a syn coplanar orientation (pointing in the same direction in
parallel planes).
3.) The metal must possess 16 total electrons or fewer and
possess an open coordination site
• For example square planar complexes of Ni, Pd and Pt.
•Tightly chelating ligands prevent opening of a coordination
site.
4.) The metal must be at least d2.

No d electrons here
1.3 SYNTHESIS
1.3 SYNTHESIS OF COMPLEXES CONTAING LIGAND

The chief methods for the synthesis of alkyls involve :

1. The R- reagent (nucleophilic attack on metal)
2. The R+ reagent (electrophilic attack on the
metal)
3. Oxidation addition
4. Insertion
 1.NUCLEOPHILIC ATTACK ON THE METAL
O Metals bearing good leaving groups are analogous to organic
electrophiles, and are susceptible to nucleophilic attack by
organolithiums, Grignard reagents, and other polarized
organometallics.
O Grignard or Organolithium reagent usually react with metal halide or
cationic metal complexes to give an alkyl, often by nucleophilic
attack on the metal.
O These reactions can be viewed as a kind of transmetalation, as the
alkyl ligand moves from one metal (Zn, Mg & Li) to another such as
transition metal.
O Electron-withdrawing X-type ligands like –Cl and –Br should jump
out as good leaving groups.
O On the other hand, clean substitution of L-type ligands by anionic
nucleophiles is much more rare (anionic complexes would result).
1. From an R- reagent (nucleophilic attack on the metal)

LiMe
(A) WCl6 WMe6 + LiCl

ZnMe2
(B) NbCl5 NbMe2Cl3 + ZnCl2
 2.ELECTROPHILIC ATTACK ON THE METAL

O Many anionic metal complexes are nucleophilic enough to attack

electrophilic sources of carbon such as alkyl and acyl halides in
an electrophilic attack mode.
O An available lone pair on the metal and open coordination site are
prerequisites ( requirement) for this chemistry.
O The charge on the complex increases by one unit (in effect, negative
charge is transferred to the electrophile’s leaving group).
O It can classify these as oxidative ligation reactions—notice that the
oxidation state of the metal increases by two units.
 2. From an R+ reagent (electrophilic attack on the metal)

MeI
(A) Mn(CO)5- MeMn(CO)5 + I-

Ph2I+
(B) CpFe(CO)2 - Cp2Fe(CO)2Ph + PhI
 3.Oxidative addition

 When addition of ligands is accompanied by oxidation of the metal,

it is called an oxidative addition reaction

L nM + X Y L n(X)(Y)M
dn dn+2
Oxidative addition OX state of metal increases by 2 units
Coordination number increases by 2 units
2 new anionic ligands are added to the metal

Requirements for oxidative addition

• availability of nonbonded electron density on the metal,

• two vacant coordination sites on the reacting complex (L nM), that
is, the complex must be coordinatively unsaturated,
• a metal with stable oxidation states separated by two units; the
higher oxidation state must be energetically accessible and stable.
 Examples of oxidative addition
How to calculate the 18
e?
-using counting electron of
common ligands.(method
B)

1. Ir come from group 9

= 1 x 9 e = 9e
2. PPh3 come from PR3 =
2 x 2 e = 4e
3. CO ligand
= 1 x 2e = 2e
4. Halide ligand
= 2 x 1e = 2 e
18e 5. CH3 =
16 e
1 x 1e = 1e
6. Total= 18e
 4.Insertion

X L
M Y [M-Y-X] M Y X
dn +L dn
No change in the formal oxidation state of the metal
O A vacant coordination site is generated during a migratory
insertion (which gets occupied by the incoming ligand)
O The groups undergoing migratory insertion must be cis to
one anoth
 O Examples of insertion

Insertion: Migration of alkyl(R) or Hydride (H) ligands from

metal center to an unsaturated ligand
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