CH2102 - VSEPR Theory and an Introduction to Coordination Chemistry

VSEPR

–

Valence Shell Electron Pair RepulsionVSEPR offers a simple method for predicting the shape of molecular compounds. The combination of

p atomic orbitals may result in σ or π molecular orbitals, similarly d atomic orbitals may form σ, π orδ molecular orbitals. These terms reflect the type of overlap between the atomic orbitals to produce

the molecular orbitals.The basis of VSEPR theory is that the shape of the molecule is determined by the repulsion between

σ valence shell electron pairs.

The electron pairs will repel each other and thus move as far from each other as possible and themolecular geometry is determined by the number of electron pairs.

VSEPR applies;

1) Only to valence shell electrons

2) To σ

bonding electrons (not π or δ)

3) To full orbital electrons (i.e. it is not applicable to unpaired electrons)

Using VSEPR Theory;

Count the number of valence electrons of the central atom2.

Add donated electrons from other atoms3.

Adjust for the charges on species4.

Calculate the total number of electrons and divide by 2 to find the number of electron pairs5.

Select the basic geometry6.

Determine which electron pairs are bonding or lone pairs7.

Modify the basic geometry to account for the electron pair interactionsIn order of increasing repulsion;bonding pair-bonding pair < bonding pair-lone pair < lone pair-lone pair

since lone pairs are localised on the central atom and act as a more concentrated source of charge than the shared bonding pairs which are less localised.

It is important to note that when describing the shape of a molecule lone pairs are not ‘visible’,

and so ammonia, NH

, is pyramidal and not tetrahedral despite its co-ordination geometry beingbased upon a tetrahedral arrangement. When determining the shape of a molecule, in the caseof several lone pairs, it is important to ensure the repulsions are minimised.

Since the coordination geometry is determined only using σ electrons it is necessary to disregard

the centra

l atom electrons involved in π or δ bonds. Since each π bond is a shared electron pairwith one electron rising from each atom, subtract one electron from each π bond involving thecentral atom. The π bond will affect the geometry, but only slightly, by pu

shing the angle to itsadjacent atoms slightly over the ideal amount.i.e. in propene the Me-C=CH

bond is 124.8⁰, slightly higher than the ideal angle of 120⁰.

As a d-orbital is essentially 2

π bonds and a σ bond, the overall effect is

-1; again its effect on thegeometry is only to push adjacent atoms slightly further than the ideal angle.For VSEPR any charge on the molecule is always assigned to the central atom, even if it wouldseem better placed elsewhere. As such a negative charge is considered an extra electron for thecentral atom, and a positive charge is shown as the subtraction of an electron from the centralatom electron count.In the case of radicals there will be a non-integral number of electron pairs, in this case theunpaired electron takes up its own orbital (i.e. 5 electrons, or 2

electron pairs would take up 3orbitals). The orbital containing the unpaired electron exerts less repulsion than it would if full,and so the bond angles change accordingly. If an electron were to be added, filling the half-filledorbital, it would then act as expected and the angles would revert to those expected.

An Introduction to Co-ordination ChemistryWerner postulated in the early 1900

’

s 3 things;1) Most elements exhibit two types of valence, a) primary valence (or

oxidation state

) and b)secondary valence (or

co-ordination number

)2) Every element tends to satisfy both its primary and secondary valence.3) The secondary valence is directed toward fixed positions in space (forming the basis of stereochemistry for metal complexes)We have since advanced this area of knowledge and as such there are several modern terms todefine;

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Coordination chemistry

–

the area concerned with structures,

reactivity’s

and physicalproperties of molecules formed by the combination of metal centres (Lewis acids) andelectron donors (Lewis bases),



Complex

–

a complex is a species formed by the association of two or more simplerspecies, each, normally, capable of independent existence



Ligand

–

a ligand is any negative ion or polar(isable) neutral molecule bound to a metalatom. This includes all Lewis bases (nucleophiles and reducing agents). Square bracketsare commonly used to denote the complex entity formed between a metal and itsligands.



Oxidation number

–

this is the charge that the central atom in a coordination compoundwould have if all of the ligands were to be removed along with the electron pairs theydonated. It is represented by a Roman numeral. Although not technically the same, theterm oxidation number is often used interchangeable with the term oxidation state (thetwo are only usually different when the ligand atom is less electronegative than thecentral atom).



Coordination number

–

commonly the number of donor atoms or ligands bound to themetal. However this definition can be misleading when more complex ligands areinvolved (such as the cyclopentadienyl ligand). It is therefore better to define thecoordination number as the number of two electron bonding pairs between a metal andits ligands (the number of coordinate bonds).



Coordination bond

–

a covalent bond in which both electrons are supplied by one of thetwo components (the ligand) of the bond.The Coordinate BondIn the case of metal-ligand interactions we use the concept of coordinate (or

dative

) bonds asdefined above.Some characteristics of a coordination bond;-coordination bonds have enthalpies of the same magnitude as those of other covalent bonds.-one atom (the ligand) donates both of the electrons involved in the bond.-the electron pair donor, or ligand, is a

Lewis base.

the electron pair acceptor (typically a metal atom or ion) is a

Lewis acid.

-the pair of electrons donated by the Lewis base is most often a lone pair.In a neutral complex the ligands are listed in alphabetical order, followed by the metal atom. Thenumber of ligands is indicated by; bi, tri, tetra, penta, hexa, hepta, octa, nona, deca etc