In chemistry, electron counting is a formalism for assigning a number of valence electrons to individual atoms in a molecule. It is used for classifying compounds and for explaining or predicting their electronic structure and bonding.[1] Many rules in chemistry rely on electron-counting:

Atoms are called "electron-deficient" when they have too few electrons as compared to their respective rules, or "hypervalent" when they have too many electrons. Since these compounds tend to be more reactive than compounds that obey their rule, electron counting is an important tool for identifying the reactivity of molecules. While the counting formalism considers each atom separately, these individual atoms (with their hypothetical assigned charge) do not generally exist as free species.

Counting rules

Two methods of electron counting are "neutral counting" and "ionic counting". Both approaches give the same result (and can therefore be used to verify one's calculation).

It is important, though, to be aware that most chemical species exist between the purely covalent and ionic extremes.

Neutral counting

E.g. in period 2: B, C, N, O, and F have 3, 4, 5, 6, and 7 valence electrons, respectively.
E.g. in period 4: K, Ca, Sc, Ti, V, Cr, Fe, Ni have 1, 2, 3, 4, 5, 6, 8, 10 valence electrons respectively.

Ionic counting

E.g. for a Fe2+ has 6 electrons
S2− has 8 electrons

Electrons donated by common fragments

Ligand Electrons contributed
(neutral counting)
Electrons contributed
(ionic counting)
Ionic equivalent
X 1 2 X; X = F, Cl, Br, I
H 1 2 H
H 1 0 H+
O 2 4 O2−
N 3 6 N3−
NR3 2 2 NR3; R = H, alkyl, aryl
CR2 2 4 CR2−2
Ethylene 2 2 C2H4
cyclopentadienyl 5 6 C5H5
benzene 6 6 C6H6

"Special cases"

The numbers of electrons "donated" by some ligands depends on the geometry of the metal-ligand ensemble. An example of this complication is the M–NO entity. When this grouping is linear, the NO ligand is considered to be a three-electron ligand. When the M–NO subunit is strongly bent at N, the NO is treated as a pseudohalide and is thus a one electron (in the neutral counting approach). The situation is not very different from the η3 versus the η1 allyl. Another unusual ligand from the electron counting perspective is sulfur dioxide.

Examples

neutral counting: C contributes 4 electrons, each H radical contributes one each: 4 + 4 × 1 = 8 valence electrons
ionic counting: C4− contributes 8 electrons, each proton contributes 0 each: 8 + 4 × 0 = 8 electrons.
Similar for H:
neutral counting: H contributes 1 electron, the C contributes 1 electron (the other 3 electrons of C are for the other 3 hydrogens in the molecule): 1 + 1 × 1 = 2 valence electrons.
ionic counting: H contributes 0 electrons (H+), C4− contributes 2 electrons (per H), 0 + 1 × 2 = 2 valence electrons
conclusion: Methane follows the octet-rule for carbon, and the duet rule for hydrogen, and hence is expected to be a stable molecule (as we see from daily life)
neutral counting: S contributes 6 electrons, each hydrogen radical contributes one each: 6 + 2 × 1 = 8 valence electrons
ionic counting: S2− contributes 8 electrons, each proton contributes 0: 8 + 2 × 0 = 8 valence electrons
conclusion: with an octet electron count (on sulfur), we can anticipate that H2S would be pseudo-tetrahedral if one considers the two lone pairs.
neutral counting: S contributes 6 electrons, each chlorine radical contributes one each: 6 + 2 × 1 = 8 valence electrons
ionic counting: S2+ contributes 4 electrons, each chloride anion contributes 2: 4 + 2 × 2 = 8 valence electrons
conclusion: see discussion for H2S above. Both SCl2 and H2S follow the octet rule - the behavior of these molecules is however quite different.
neutral counting: S contributes 6 electrons, each fluorine radical contributes one each: 6 + 6 × 1 = 12 valence electrons
ionic counting: S6+ contributes 0 electrons, each fluoride anion contributes 2: 0 + 6 × 2 = 12 valence electrons
conclusion: ionic counting indicates a molecule lacking lone pairs of electrons, therefore its structure will be octahedral, as predicted by VSEPR. One might conclude that this molecule would be highly reactive - but the opposite is true: SF6 is inert, and it is widely used in industry because of this property.
neutral counting: Ti contributes 4 electrons, each chlorine radical contributes one each: 4 + 4 × 1 = 8 valence electrons
ionic counting: Ti4+ contributes 0 electrons, each chloride anion contributes two each: 0 + 4 × 2 = 8 valence electrons
conclusion: Having only 8e (vs. 18 possible), we can anticipate that TiCl4 will be a good Lewis acid. Indeed, it reacts (in some cases violently) with water, alcohols, ethers, amines.
neutral counting: Fe contributes 8 electrons, each CO contributes 2 each: 8 + 2 × 5 = 18 valence electrons
ionic counting: Fe(0) contributes 8 electrons, each CO contributes 2 each: 8 + 2 × 5 = 18 valence electrons
conclusions: this is a special case, where ionic counting is the same as neutral counting, all fragments being neutral. Since this is an 18-electron complex, it is expected to be isolable compound.
neutral counting: Fe contributes 8 electrons, the 2 cyclopentadienyl-rings contribute 5 each: 8 + 2 × 5 = 18 electrons
ionic counting: Fe2+ contributes 6 electrons, the two aromatic cyclopentadienyl rings contribute 6 each: 6 + 2 × 6 = 18 valence electrons on iron.
conclusion: Ferrocene is expected to be an isolable compound.


See also

References

  1. ^ Parkin, Gerard (2006). "Valence, Oxidation Number, and Formal Charge: Three Related but Fundamentally Different Concepts". Journal of Chemical Education. 83 (5): 791. Bibcode:2006JChEd..83..791P. doi:10.1021/ed083p791. ISSN 0021-9584. Retrieved 2009-11-10.
  2. ^ Green, M. L. H. (1995-09-20). "A new approach to the formal classification of covalent compounds of the elements". Journal of Organometallic Chemistry. 500 (1–2): 127–148. doi:10.1016/0022-328X(95)00508-N. ISSN 0022-328X.
  3. ^ "MLXZ". www.columbia.edu.