NAJIHAH BINTI MAZLAN 172070

NURUL ATIFAH BINTI ANSARUDIN 173051

BAZILAH BINTI AHMAD 173507
NURSYAMIMI IZZATY BINTI MOHD YUSOFF 174425
NUR SHAQINAH BINTI MUSTAFA 175175
 Organometallic ligand.
 L-type ligand : neutral ligands that donate two electrons to the metal center.
 Many phosphine-containing complexes do not possess 18 valence electrons.
 Chelating or polydentate ligand
 CHARACTERISTIC OF PHOSPHINE
May ignite
Reactive
spontaneously on
contact with air at or
about 100°C.

Spontaneously
flammable in air, Flammable Phosphine Poisonous
gas
Noxious and
burning with a (PH3)
luminous flame harmful
substance
s
Dissolve
more
Due to non- readily in
polar P-H bonds non-polar
solvent
 Colorless gas with an odour of rotten fish
 Phosphine molecule is pyramidal like the molecule of ammonia
 Slightly soluble in water
 No reaction with acids or alkalies
 Lower boiling point
 Behaves as a powerful reducing agent
 Can act as:
1) σ donor: have lone pair on the P atom that is appreciably basic and nucleophilic.
2) π acceptor: have empty orbital on the P atom that can overlap with filled d orbital on
3d-metal ions.
 However, Ph3 is rarely used as ligand.
 Substituted phosphines that are widely used as ligands :
 Trialkylphosphines (PMe3, PEt3)
 Triarylphosphines (PPh3)
 Trialkyl or triarylphosphites (P(Ome)3)
 A whole host of bridged multidentate di- and triphosphines
 Alkylphosphines, which possess P–Csp3 bonds, are better electron donors than
arylphosphines, which possess P–Csp2 bonds.
 Electronegativity of the sp2 hybrid orbital are stronger.
 These idea applies when electron-withdrawing and -donating groups are incorporated
into R: the electron density on P is low when R contains electron-withdrawing groups
and high when R contains electron-donating groups.
• In tertiary phosphines (PR3), when R group becomes more electronegative, both of the σ
and the σ* orbital of the P−R bond becomes more stable (lower in energy).
• At the same time, the phosphorus contribution to σ* orbital increases, and so the size
of the σ* lobe that points toward the metal increases.
• Both of these factors make the empty σ* more accessible for π-back donation (better
acceptor of electron density from the metal centre and better overlap of the σ* orbital of
the P−R bond with the metal dπ orbital).
 Bonding similar to CO.
 Phosphine bond to metal by combination of σ-donation from P atom and π-back bonding
from metal atom.
 Occupation of the P−R σ* orbital by back donation from
the metal also suggest that the P−R bonds should
lengthen slightly on binding.
 But, in reality, this is hidden by a simultaneous shortening
of the P−R bond due to donation of the P lone pair to the
metal, and the consequent decrease in P(lone pair)–
R(bonding pair) repulsions
 The M−L π bond is made at the expense of a bond in the
ligand, using σ bond.
 Used to determine the steric properties of phosphine and their coordination
behaviour.
 Bulky ligands, there are steric repulsion with each other when packed around metal.
Thus, they favor dissociative activation (reaction in which an intermediate of reduced
coordination number is formed by the departure of the leaving group) and inhibit
associative activation (reaction in which an intermediate of higher coordination
number is formed).
 This was due to larger ligand bump to each other and stay far away from metal that
causes poor bonding.
 Measured by folding back the R substituents as far as they will go, and measuring the
angle of the cone that will just contain all of the ligand, with the apex of the cone is at
the metal.
 Only a certain number of phosphines can fit around the metal.

Usual maximum number of phosphines that

two for PCy3 or P(i-Pr)3

can bind to a single metal

three or four for PPh3

four for PMe2Ph

five or six for PMe3

 For example, nickel would like to have four ligands in order to have an eighteen
electron configuration, but because of the large cone angles that are present at the
phosphorus it is not possible to pack four of them.
 Increase the size of the ligand causes complexes to dissociate one of the ligands
easily but dissociation constant is not.
 As bulk increases the dissociation constant also increases.
 The diastereoisomers of menthylphosphinite boranes are popular synthetic intermediates.
 Nucleophilic substitution of pure diastereomer (RP)-2a with methyllithium afforded the phosphine–
borane (S)-4 with 94% enantiomeric excess. The substitution resulted in inversion of the
configuration at the phosphorus center.
 Deboranation of the air stable borane adduct (S)-4 to obtain 5, was achieved by treatment with N-
methylpyrrolidine.
EXAMPLE : Synthesis of complexes containing the phosphine
ligand - Tris(phosphaalkene)phosphine Ligand

Advantages of this ligand

 Steric control - to prevent oligomerization of the P=C fragment
 Introducing electronic component - capable of enhancing reactivity
through redox-active/noninnocent processes.
 Prepared by well-precedented phospha-Wittig

Where:

Mes* = 2,4,6-tri-tert-butylbenzene
SYNTHESIS OF Rh(I) AND Ir(I) CHLORIDE COMPLEXES

 Ligand 1 acting as a multidentate ligand to a single metal center.

 Addition of a solution of 1 in benzene to 0.5 equivalent of [RhCl(C2H4)2]2 resulted
in the generation of trigonal bipyramidal Rh(I) of complex 2a.
SUBSTITUTION ON Rh(I) COMPLEXES – 2A
HALIDE ABSTRACTION ON Ir(I) COMPLEXES – 2B
Most of phosphine-complexes do not possess 18 valence electrons.
+ Phospine-complexes are polydentate ligand
+ Phosphine that P–Csp3 bonds are better electron donors than phosphine which possess P–
Csp2 bonds (EDG/EWG concept)
1) Crabtree, R. (2014). The organometallic chemistry of the transition metals (1st
ed.). Hoboken, New Jersey: Wiley.
2) Atkins, Peter William, Tina Overton, Jonathan Rourke, Mark Weller, Fraser A.
Armstrong, and D. F. Shriver (2006). Shriver & Atkins Information Retrieval. 5th
ed. Oxford: Oxford UP, Print.
3) http://alpha.chem.umb.edu/chemistry/ch611/documents/Lec6-
CarbonylandPhosphineLigands.pdf