Steric effects

Short description: Geometric aspects of ions and molecules affecting their shape and reactivity

The parent cyclobutadiene (R = H) readily dimerizes but the R = tert-butyl derivative is robust.[1]

Steric effects arise from the spatial arrangement of atoms. When atoms come close together there is generally a rise in the energy of the molecule. Steric effects are nonbonding interactions that influence the shape (conformation) and reactivity of ions and molecules. Steric effects complement electronic effects, which dictate the shape and reactivity of molecules. Steric repulsive forces between overlapping electron clouds result in structured groupings of molecules stabilized by the way that unlike charges attract and like charges repel.

## Contents

* 1 Steric hindrance
* 2 Measures of steric properties
* 2.1 Rate data
* 2.2 A-values
* 2.3 Ceiling temperatures
* 2.4 Cone angles
* 3 Significance and applications
* 4 See also
* 5 References
* 6 External links

## Steric hindrance

Regioselective dimethoxytritylation of the primary 5'-hydroxyl group of thymidine in the presence of a free secondary 3'-hydroxy group as a result of steric hindrance due to the dimethoxytrityl group and the ribose ring (Py = pyridine).[2]

Steric hindrance is a consequence of steric effects. Steric hindrance is the slowing of chemical reactions due to steric bulk. It is usually manifested in intermolecular reactions, whereas discussion of steric effects often focus on intramolecular interactions. Steric hindrance is often exploited to control selectivity, such as slowing unwanted side-reactions.

Steric hindrance between adjacent groups can also affect torsional bond angles. Steric hindrance is responsible for the observed shape of rotaxanes and the low rates of racemization of 2,2'-disubstituted biphenyl and binaphthyl derivatives.

## Measures of steric properties

Because steric effects have profound impact on properties, the steric properties of substituents have been assessed by numerous methods.

### Rate data

Relative rates of chemical reactions provide useful insights into the effects of the steric bulk of substituents. Under standard conditions, methyl bromide solvolyzes 107 faster than does neopentyl bromide. The difference reflects the inhibition of attack on the compound with the sterically bulky (CH3)3C group.[3]

### A-values

A-values provide another measure of the bulk of substituents. A-values are derived from equilibrium measurements of monosubstituted cyclohexanes.[4][5][6][7] The extent that a substituent favors the equatorial position gives a measure of its bulk.

File:Methyl group cyclohexane.svg The A-value for a methyl group is 1.74 as derived from the chemical equilibrium above. It costs 1.74 kcal/mol for the methyl group to adopt to the axial position compared to the equatorial position. Substituent | A-value

|

H | 0
CH3 | 1.74
CH2CH3 | 1.75
CH(CH3)2 | 2.15
C(CH3)3 | >4

### Ceiling temperatures

Ceiling temperature (Tc) is a measure of the steric properties of the monomers that comprise a polymer. Tc is the temperature where the rate of polymerization and depolymerization are equal. Sterically hindered monomers give polymers with low Tc's, which are usually not useful.

Monomer | Ceiling temperature (°C)[8] | Structure

|
|

ethylene | 610 | CH2=CH2
isobutylene | 175 | CH2=CMe2
1,3-butadiene | 585 | CH2=CHCH=CH2
isoprene | 466 | CH2=C(Me)CH=CH2
styrene | 395 | PhCH=CH2
α-methylstyrene | 66 | PhC(Me)=CH2

### Cone angles

Ligand cone angle.

Ligand cone angles are measures of the size of ligands in coordination chemistry. It is defined as the solid angle formed with the metal at the vertex and the hydrogen atoms at the perimeter of the cone (see figure).[9]

Cone angles of common phosphine ligands  Ligand | Angle (°)

|

PH3 | 87
P(OCH3)3 | 107
P(CH3)3 | 118
P(CH2CH3)3 | 132
P(C6H5)3 | 145
P(cyclo-C6H11)3 | 179
P(t-Bu)3 | 182
P(2,4,6-Me3C6H2)3 | 212

## Significance and applications

Steric effects are critical to chemistry, biochemistry, and pharmacology. In organic chemistry, steric effects are nearly universal and affect the rates and activation energies of most chemical reactions to varying degrees. In some cases, steric effects are necessary to ensure a molecule's stability. In Günther Maier's corset effect, bulky substituents stabilize a molecular core because decomposition would force the substituents closer together.[10] Conversely, substituent attraction can stabilize molecules; these molecules are called "dispersion-stabilized".

In biochemistry, steric effects are often exploited in naturally occurring molecules such as enzymes, where the catalytic site may be buried within a large protein structure. In pharmacology, steric effects determine how and at what rate a drug will interact with its target bio-molecules.

* Prominent sterically hindered compounds
* Tris(2,4-di-tert-butylphenyl)phosphite, a widely used stabilizer in polymers.

* Tricyclohexylphosphine, a bulky phosphine ligand used in homogeneous catalysis and, with B(C6F5)3, comprises the classic frustrated Lewis pair.[11]

* 2,6-Di-tert-butylphenol is used industrially as UV stabilizers and antioxidants for hydrocarbon-based products ranging from petrochemicals to plastics.[12]

* Hindered amine light stabilizers are widely used in polymers.[13][14]

* Titanium isopropoxide is a monomer, the corresponding titanium ethoxide is a tetramer.

* An isolable selenenic acid owing to steric protection.[15]

The steric effect of tri-(tert-butyl)amine makes electrophilic reactions, like forming the tetraalkylammonium cation, difficult. It is difficult for electrophiles to get close enough to allow attack by the lone pair of the nitrogen (nitrogen is shown in blue)

## See also

* Collision theory
* Intramolecular force
* Sterically induced reduction
* Reaction rate accelerate as result of steric hindrance in the Thorpe–Ingold effect
* Van der Waals strain, also known as steric strain

## References

1. ↑ Günther Maier; Stephan Pfriem; Ulrich Schäfer; Rudolf Matusch (1978). "Tetra-tert-butyltetrahedrane". Angew. Chem. Int. Ed. Engl. 17 (7): 520–1. doi:10.1002/anie.197805201.
2. ↑ Gait, Michael (1984). Oligonucleotide synthesis: a practical approach. Oxford: IRL Press. ISBN 0-904147-74-6.
3. ↑ Smith, Michael B.; March, Jerry (2007), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (6th ed.), New York: Wiley-Interscience, ISBN 978-0-471-72091-1, https://books.google.com/books?id=JDR-nZpojeEC&printsec=frontcover
4. ↑ E.L. Eliel, S.H. Wilen and L.N. Mander, Stereochemistry of Organic Compounds, Wiley, New York (1994). ISBN 81-224-0570-3
5. ↑ Eliel, E.L.; Allinger, N.L.; Angyal, S.J.; G.A., Morrison (1965). Conformational Analysis. New York: Interscience Publishers.
6. ↑ Hirsch, J.A. (1967). Topics in Stereochemistry (first ed.). New York: John Wiley & Sons, Inc.. p. 199.
7. ↑ Romers, C.; Altona, C.; Buys, H.R.; Havinga, E. (1969). Topics in Stereochemistry (fourth ed.). New York: John Wiley & Sons, Inc.. p. 40.
8. ↑ Stevens, Malcolm P. (1999). "6". Polymer Chemistry an Introduction (3rd ed.). New York: Oxford University Press. pp. 193–194. ISBN 978-0-19-512444-6.
9. ↑ Tolman, Chadwick A. (1970-05-01). "Phosphorus ligand exchange equilibriums on zerovalent nickel. Dominant role for steric effects". J. Am. Chem. Soc. 92 (10): 2956–2965. doi:10.1021/ja00713a007. Bibcode: 1970JAChS..92.2956T.
10. ↑ Maier, G.; Pfriem, S.; Schäfer, U.; Matusch, R. (1978). "Tetra-tert-butyltetrahedrane". Angew. Chem. Int. Ed. Engl. 17 (7): 520–521. doi:10.1002/anie.197805201.
11. ↑ Stephan, Douglas W. "Frustrated Lewis pairs": a concept for new reactivity and catalysis. Org. Biomol. Chem. 2008, 6, 1535–1539. doi:10.1039/b802575b
12. ↑ Helmut Fiege; Heinz-Werner Voges; Toshikazu Hamamoto; Sumio Umemura; Tadao Iwata; Hisaya Miki; Yasuhiro Fujita; Hans-Josef Buysch et al. (2002). "Phenol Derivatives". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. pp. a19_313. doi:10.1002/14356007.a19_313. ISBN 3-527-30673-0.
13. ↑ Pieter Gijsman (2010). "Photostabilisation of Polymer Materials". in Norman S. Allen. Photochemistry and Photophysics of Polymer Materials Photochemistry. Hoboken: John Wiley & Sons. pp. 627–679. doi:10.1002/9780470594179.ch17. ISBN 978-0-470-59417-9. .
14. ↑ Klaus Köhler; Peter Simmendinger; Wolfgang Roelle; Wilfried Scholz; Andreas Valet; Mario Slongo (2010). "Paints and Coatings, 4. Pigments, Extenders, and Additives". Ullmann's Encyclopedia Of Industrial Chemistry. pp. o18_o03. doi:10.1002/14356007.o18_o03. ISBN 978-3-527-30673-2.
15. ↑ Goto, Kei; Nagahama, Michiko; Mizushima, Tadashi; Shimada, Keiichi; Kawashima, Takayuki; Okazaki, Renji (2001). "The First Direct Oxidative Conversion of a Selenol to a Stable Selenenic Acid: Experimental Demonstration of Three Processes Included in the Catalytic Cycle of Glutathione Peroxidase". Organic Letters 3 (22): 3569–3572. doi:10.1021/ol016682s. PMID 11678710.

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