Phosphines (PR3) : Neutral Spectator Ligands

• Spectator ligands are ligands which are present on the metal centre but do not
take part in a reaction.
• Their properties (mainly steric and electronic) alter the reactivity of the metal
centre.
• Phosphines are some of the most widely used spectator ligands.

Phosphines (PR3) are excellent soft donor ligands (which are large and
polarisable) with a variety of substituents which differ in steric and
electronic properties. Variation of three R groups can effect:
• Significant change in the steric size of the phosphine
• Change in the basicity and nucleophilicity of the phosphine
• generation of a large number of multidentate polyphosphines (bis-,
tris-, tetra-, penta-, and hexaphosphine ligands are all known) that
can adopt specific coordination geometries as well as
stereochemistry.

• Triphenylphosphine (PPh3) is the most widely used monodentate phosphine as it

is air and moisture stable.
• Almost all alkyl phosphines are fairly to highly air-sensitive, get oxidised to
phosphine oxide on exposure to air.
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The electron-donating ability of a phosphine ligand was determined by reacting one equivalent
of the phosphine (monodentate) with Ni(CO)4 to make a Ni(CO)3(phosphine) complex.

PR3 CO (cm-1) PR3 CO (cm-1)

P(t-Bu)3 2056.1 PPh2(C6F5) 2074.8
PCy3 2056.4 P(O-i-Pr)3 2075.9
P(i-Pr)3 2059.2 P(OEt)3 2076.3
PEt3 2061.7 PPhH2 2077.0
PMe3 2064.1 P(OMe)3 2079.5
PBz3 2066.4 PPh(OPh)2 2079.8
P(o-Tol)3 2066.6 PPh2Cl 2080.7
PMePh2 2067.0 PH3 2083.2
P(m-Tol)3 2067.2 P(OPh)3 2085.3
PPh3 2068.9 P(C6F5)3 2090.9
P(p-C6H4-F)3 2071.3 PCl3 2097.0
PPh2H 2073.3 PF3 2110.8

59
 Basicity of Phosphines
• The pKa values are typically
used as a measure of σ
donor capability of a
phosphines

• Generally, phosphines are

less basic compared to
amines
pKa of NEt3 = 10.87
pKa of PEt3 = 8.69

• There are many examples

of reactions where a less
electron donating
phosphine is displaced by
more electron donating
phosphine.

Grubbs’ First
Generation
Catalyst
60
 Different types of Phosphines
Me
Me Me
Me Me Me PR2 PCy2
MeO OMe
Me P Me
Me P Bu R=Cy, t-Bu
Sterically hindered and electron rich tertiary phosphines

Biphosphines Chiral Phosphines 61

 Carbenes as Ligands (:CR2)
• Carbenes are species which are highly reactive and rarely stable in free state.
• There are two types of carbenes-singlet (↑↓) and triplet (↑↑) carbenes.
• Two types of metal carbenes : Fischer Carbene and Schrock Carbene.

Fischer Carbene Complexes

✓ Metal is in a low oxidation state (electron rich) and bonding of the carbene is similar
to that of CO.
✓ Metal stabilized by electron accepting ligands
✓ Carbene is more close to singlet carbene
✓ Carbon is electron deficient (stabilized by heteroatoms/phenyl groups)
✓ M=C bond is relatively weak and have low rotational barrier
Synthesis
O-Li+ OMe
LiR Me3O+BF4-
(CO)5W-CO (CO)5W C (CO)5W C W(+2) – d4
R R
Fischer Carbene

Cr(+2) – d4 Fe(+2) – d6
Pt(+4) – d6

Other Examples of Fischer Carbene Complexes 62

Schrock Carbene Complexes
✓ Metal is in a high oxidation state (electron
deficient and stabilized by electron
donating ligands)
✓ Carbene is more close to triplet carbene
✓ Carbon is electron rich (destabilized by
heteroatoms groups)
✓ M=C bond is relatively strong and have
large rotational barrier
Ta(+5)-d0 Ta(+5)- d0
Examples of Schrock Carbene
Complexes
In the Fischer Carbene, donation of
electrons from the carbon to the metal
dominates (with some amount of back
donation to the carbene carbon’s p
orbital) leaving the carbene carbon
atom with a slightly positive charge.
In the Schrock Carbene, two covalent
bonds are envisaged between the
metal and carbon, both of them
polarised towards the carbon, giving it
a slight negative charge.
Alternately, the schrock carbene can be
considered as a Fischer carbene with
very strong back donation.
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 N-HETEROCYCLIC CARBENES (NHCs)

• Typically, normal carbenes are very reactive and

short lived molecules that cannot be isolated. But
NHCs are quite stable.
• NHCs are imidazolidine ligands with sterically
encumbering groups such as mesityl, isopropyl
and admantyl, etc
• They are attractive alternatives to tertiary
phosphine ligands. [Phosphines-high cost(chiral),
sensitive to oxidation, etc].

Advantages of NHC:
• They are stronger donor than phosphines.
• The stronger M-C bond of the NHC complexes
favours reaction kinetics which involves less of NHC
dissociation from the metal complex
• The presence of sterically hindered groups bound to N atoms facilitate reductive
elimination of the product from the metal during catalysis.
• Their activity can be modified by introducing electronically different substituents on
the nitrogen atoms in the ring.
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N-HETEROCYCLIC CARBENES and Olefin Metathesis Catalysts

Grubbs first generation catalyst as well as second generation catalyst, have

properties intermediate between Fischer and Schrock type carbenes.
65
 Q1. Classify the following carbenes as Fischer type, Schrock type or the
one in between the two.

Ans. A and B are Fischer type, C and D are Schrock type and E is in between the
two.

66
Unique reactions in organometallic chemistry

➢ Oxidative Addition

➢ Reductive Elimination

➢ Migratory Insertion

➢  - Hydrogen Elimination

67
 Oxidative addition
When addition of ligands is accompanied by oxidation of the metal, it is called an
oxidative addition reaction
LnM + XY Ln(X)(Y)M Often the first step of the mechanism
dn dn-2

• OX state of metal increases by 2 units H2 oxidative

H
Ph3P PPh3 addition H PPh3
• Coordination number increases by 2 units Rh Rh
Ph3P Cl Ph3P Cl
• 2 new anionic ligands are added to the metal PPh3
Rh+1 Rh+3

Wilkinson’s Catalyst

Requirements for oxidative addition

✓ availability of nonbonded electron density on the metal,

✓ two vacant coordination sites on the reacting complex (LnM), 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.

68
 Examples of Oxidative addition : Cis or trans ?
Depending on the nature of the adding group (polar, nonpolar) as well as the type of
mechanism involved (concerted, SN2, free radical and ionic) one can get either cis
addition products, a mixture of cis and trans addition products or in few cases trans
addition products.

Homonuclear systems (H2, Cl2, O2, C2H2) Cis

Heteronuclear systems (MeI) Cis or trans
VASKA’s Complex

Note:
• d0 metals cannot undergo oxidative additions So always electron count the starting
and final metal complexes to check out the overall electron-count, metal oxidation
state and d-electron count.
• Compounds with 18 electrons cannot undergo oxidative addition without the
expulsion of a ligand.
e.g Ru(CO)4(PMe3) + MeI gives Ru(CH3)(I)(CO)3(PMe3) + CO
69
 Intramolecular Oxidative Addition: C-H Activation and
cyclo/ortho metallation

Agostic interaction

Oxidative Coupling

Ph2 Cl
Ph2 Cl
P
P H3C N Cr
H3C N Cr
P
P Ph2 Cl
Ph2 Cl
Cr(+5) d1
Cr(+3) d3
13e-
15e-

70
 Reductive elimination
Almost the exact reverse of Oxidative Addition

CH3 Ph2
Ph2
P CH3 P CH3
reductive elimination + H3C CH3
Pt Pt
165 °C, days P CH3
P CH3
Ph2 Ph2
CH3
Pt4+ Pt2+

Oxidation state of metal decreases by 2 units

Coordination number decreases by 2 units
2 cis oriented anionic ligands form a stable  bond and leave the metal

Factors which facilitate reductive elimination

• a high formal positive charge on the metal,
• the presence of bulky groups on the metal, and
• an electronically stable organic product.

Cis orientation of the groups taking part in reductive elimination is a MUST

Final step in many catalytic cycles 71

 Migratory Insertion
X L
+L
M Y [M-Y-X] M Y X
dn dn
No change in the formal oxidation state of the metal
A vacant coordination site is generated during a migratory insertion (which gets occupied by
the incoming ligand)

The groups undergoing migratory insertion must be cis to one another

CH3 Ph3P O
OC OC
CO C
Mn + PPh3 Mn CH3
OC CO OC CO
OC OC

These reactions are enthalpy driven and although the reaction is entropy
prohibited the large enthalpy term dominates
72
 Types of Migratory Insertion
X
X
X = Anionic
M A B M A 1, 1 - migratory insertion
ligand = H, R,
B Ar, COR
X
X
A AB = Neutral
B 1, 2 - migratory insertion ligand = CO,
M
M A alkene, alkyne
B

CO O
CH2CH2R 1, 1-migratory Ph P CCH2CH2R
Ph3P insertion 3
Rh Rh
OC PPh3 OC PPh3

H
R 1, 2-migratory CH2CH2R
Ph3P
Ph3P insertion
Rh Rh
Ph3P OC PPh3
CO
73
 Migration versus Insertion

A migration occurs when

the anionic ligand moves
and performs a
nucleophilic-like
intramolecular attack on
the electrophilic neutral
legand.

An insertion occurs when

the neutral ligand moves
and gets inserted into the
bond between the metal
and the anionic ligand.

Most systems studies have been shown to undergo migration and not insertions.

74
 -Hydride elimination
Beta-hydride elimination is a reaction in which an alkyl group having a  hydrogen,  bonded
to a metal centre is converted into the corresponding metal-bonded hydride and a  bonded
alkene. The alkyl must have hydrogens on the beta carbon. For instance butyl groups can
undergo this reaction but methyl groups cannot. The metal complex must have an empty (or
vacant) site cis to the alkyl group for this reaction to occur.

No change in the formal oxidation state of the metal

mechanism H H H H H
H H H
C H C C
M
M C M C C
H H H H H H

Can either be a vital step in a reaction or an unwanted side reaction

75
 -hydrogen elimination does not happen when
• the alkyl has no -hydrogen (as in PhCH2, Me3CCH2, Me3SiCH2)
• the -hydrogen on the alkyl is unable to approach the metal (as in C≡CH)
• the M–C–C–H unit cannot become coplanar

Question: Select the most unstable platinum  complex from the given list. Justify
your answer

H
Ph3P C Ph3P Ph3P
SiMe3 Et3P C
Pt Pt Pt Pt
Ph3P SiMe3 Ph3P Ph3P
Et3P C
C
H
A B C D

No  -H  -H unable to MCCH unit will not be

approach M coplanar

76
 Problem solving
Classify the following reactions as oxidative addition,
reductive elimination, (1,1 / 1,2)migratory insertion, - H
elimination, ligand coordination change or simple addition

(a) [RhI3(CO)2CH3]− → {RhI3(CO)( solvent)[C(O)CH3]}−

(b) Ir(PPh2Me)2(CO)Cl + CF3I → Ir(I)(CF3)(PPh2Me)2(CO)Cl

(c) TiCl4 +2 Et3N → TiCl4 (NEt3)2

(d) HCo(CO)3(CH2=CHCH3) + CO → CH3CH2CH2Co(CO)4

Step 1. determine the oxidation state of the metal in reactant and
product
Step 2. count the electrons for reactant and product
Step 3. see if any ligand in the reactant has undergone change
Answer: (a) 1,1- Migratory insertion; (b) Oxidative addition; (c) Simple addition;
(d) 1,2- Migratory insertion 77
Question:

Answer: (a)
78