Steric interaction/repulsion

The parameter redundancy is also the reason that care should be exercised when trying to decompose energy differences into individual terms. Although it may be possible to rationalize the preference of one conformation over another by for example increased steric repulsion between certain atom pairs, this is intimately related to the chosen functional form for the non-bonded energy, and the balance between this and the angle bend/torsional terms. The rotational banier in ethane, for example, may be reproduced solely by an HCCH torsional energy term, solely by an H-H van der Waals repulsion or solely by H-H electrostatic repulsion. Different force fields will have (slightly) different balances of these terms, and while one force field may contribute a conformational difference primarily to steric interactions, another may have the... 

Structures 5 and 6 display the solid state structures of two representative distibine and dibismuthine adducts. The ligands bound to the central Sb and Bi atoms adopt a staggered conformation in relation to one another, with the bulky M(t-Bu)3 groups arranged in a trans-position. This is likely due to repulsive steric interactions. The central Sb—Sb [281.1(1) 32 283.9(1) pm 35] and Bi—Bi bond distances [298.3(1) 36 and 298.4(1) pm 37] are almost unchanged compared to the uncomplexed distibines and dibismuthines, as can be seen... 

The surface forces apparatus (SEA) can measure the interaction forces between two surfaces through a liquid [10,11]. The SEA consists of two curved, molecularly smooth mica surfaces made from sheets with a thickness of a few micrometers. These sheets are glued to quartz cylindrical lenses ( 10-mm radius of curvature) and mounted with then-axes perpendicular to each other. The distance is measured by a Fabry-Perot optical technique using multiple beam interference fringes. The distance resolution is 1-2 A and the force sensitivity is about 10 nN. With the SEA many fundamental interactions between surfaces in aqueous solutions and nonaqueous liquids have been identified and quantified. These include the van der Waals and electrostatic double-layer forces, oscillatory forces, repulsive hydration forces, attractive hydrophobic forces, steric interactions involving polymeric systems, and capillary and adhesion forces. Although cleaved mica is the most commonly used substrate material in the SEA, it can also be coated with thin films of materials with different chemical and physical properties [12]. 

The enamines derived from cyclohexanones are of particular interest. The pyrrolidine enamine is most frequently used for synthetic applications. The enamine mixture formed from pyrrolidine and 2-methylcyclohexanone is predominantly isomer 17.106 A steric effect is responsible for this preference. Conjugation between the nitrogen atom and the tt orbitals of the double bond favors coplanarity of the bonds that are darkened in the structures. In isomer 17 the methyl group adopts a quasi-axial conformation to avoid steric interaction with the amine substituents.107 A serious nonbonded repulsion (A1,3 strain) in 18 destabilizes this isomer. 

In comparison with the decomposition of taws-azoalkanes 20 a much larger group size effect has been found for the thermolysis rates of a few c/s-azoalkanes 24. Due to the repulsion of the free electron pairs on the two nitrogen atoms and due to steric interaction between the cis oriented alkyl groups cis azoalkanes 24 decom-... 

Figure 7 displays the data of Ito4,13 and others29 in a 3 x 3 matrix of torsional potentials for o-fluorotoluene, m-fluorotoluene, and p-fluorotoluene in the three electronic states S0, S, and D0. The matrix reveals patterns that hold for other ortho, meta, and para substituents as well.9 In S0, ortho substitution creates a large barrier, while meta substitution does not. A sensible interpretation invokes steric repulsion between methyl and the ortho substituent. Hie menz-substituted cases have very small barriers like toluene itself, apparently for lack of steric effects. However, in ort/io-substituted toluenes, V3 decreases sharply on ji — n excitation from S0 to S, while in mefa-substituted toluenes, V3 increases substantially from S0 to S,. This suggests that steric interactions are not the complete story. Most intriguing of all,... 

In this section, we present a unified picture of the different electronic effects that combine to determine methyl rotor potentials in the S0, Sp and D0 electronic states of different substituted toluenes. Our approach is based on analysis of ab initio wavefunctions using the natural bond orbitals (NBOs)33 of Weinhold and cowork-ers. We will attempt to decompose the methyl torsional potential into two dominant contributions. The first is repulsive steric interactions, which are important only when an ortho substituent is present. The second is attractive donor-acceptor interactions between CH bond pairs and empty antibonding orbitals vicinal to the CH bonds. In the NBO basis, these attractive interactions dominate the barrier in ethane (1025 cm-1) and in 2-methylpropene (1010 cm-1) see Figure 3. By analogy, donor-acceptor attractions are important in toluenes whenever there is a substantial difference in bond order between the two ring CC bonds adjacent to the C-CH3 bond. Viewed the other way around, we can use the measured methyl rotor potential as a sensitive probe of local ring geometry. 

In the case of catalyst 3, the thiophene substitution in the 6,7 position controls the gap aperture between fluorenyl and indenyl ligands by repulsing steric interactions at the complex backside [10, 11]. This leads to increased stereoselectivities [9] and is responsible for a C2-symmetric-like polymerization mechanism, characterized by increasing isotacticities when the polymerization temperature is reduced [5, 11] (Fig. 7). 

Steric interactions between bulky substituents such as t-Bu, leading to larger C-E-C bond angles, obviously affect the Lewis basicity caused by the increased -character of the electron lone pair. However, the strength of the Lewis acid-base interaction within an adduct as expressed by its dissociation enthalpy does not necessarily reflect the Lewis acidity and basicity of the pure fragments, because steric (repulsive) interactions between the substituents bound to both central elements may play a contradictory role. In particular, adducts containing small group 13/15 elements are very sensitive to such interactions as was shown for amine-borane and -alane adducts... 

The observed tendencies for the Bu3Al <— ER 3 adducts clearly reflect the influence of repulsive steric interactions between the large t-Bu and z-Pr substituents which become less important with increasing atomic radius of the central pentele. Such interactions overcompensate attractive dipolar... 

The planar conformations s-cis and s-trans cannot be appreciably populated owing to the repulsive steric interaction between the Cg—H and C5-methyl (in the s-cis) or between the same Cg—II and the methyl group on (Q in the s-trans). This repulsion is minimized by introducing a twist around the Q,—( 7 bond. Limiting conformations, with skew angles of about 40° and 140°, can be assumed, as shown in Scheme 8. In this way, an intrinsically dissymmetric chromophore is created. 

Primary steric effects are due to repulsions between electrons in valence orbitals on atoms which are not bonded to each other. They are believed to result from the interpenetration of occupied orbitals on one atom by electrons on the other resulting in a violation of the Pauli exclusion principle. All steric interactions raise the energy of the system in which they occur. In terms of their effect on chemical reactivity, they may either decrease or increase a rate or equilibrium constant depending on whether steric interactions are greater in the reactant or in the product (equilibria) or transition state (rate). 

The asymmetric induction cannot be explained simply by steric interaction because the R group in the aldehyde is far too remote to interact with the tartrate ester. In addition, the alkyl group present in the tartrate ligand seems to have a relatively minor effect on the overall stereoselectivity. It has thus been proposed that stereoelectronic interaction may play an important role. A more likely explanation is that transition state A is favored over transition state B, in which an n n electronic repulsion involving the aldehyde oxygen atom and the /Mace ester group causes destabilization (Fig. 3-6). This description can help explain the stereo-outcome of this type of allylation reaction. 

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