X Bonds

We ai e free to pick a tefei ence poitit of energy once, but otily otice, for each system, l,et us choose the reference point t.. We have obtained the energy eigenvalues of the x bond in ethylene as one [f greater than y. 011)11 bunding) and one p lower than y ( bunding) (Fig, 6-3),... 

Conceptually the most simple syntheses of complex molecules involve the joining of structural units in which all functional groups and all asymmetric centres are preformed. This technique can usually only be applied to compounds in which these units are connected by —C—X— bonds rather than C—C. It is illustrated here by the standard syntheses of oligonucleotides, peptides, and polydentate macrocyclic ligands. 

The strength of an acid depends on the atom to which the proton is bonded The two mam factors are the strength of the H—X bond and the electronegativity of X Bond strength is more important for atoms m the same group of the periodic table electronegativity is more important for atoms m the same row Electronegative atoms elsewhere m the molecule can increase the acidity by inductive effects... 

Aryl halides are less reactive than alkyl halides m reactions m which C—X bond breaking is rate determining especially m nucleophilic sub stitution reactions... 

The group moment always includes the C—X bond. When the group is attached to an aromatic system, the moment contains the contributions through resonance of those polar structures postulated as arising through charge shifts around the ring. 

The properties and applications of commercially important hydride functional silanes, ie, compounds having a Si—H bond halosilanes, ie, compounds having a Si—X bond and organosilanes, ie, compounds having a Si—C bond, are discussed hereia. Compounds having Si—OSi bonds are called sdoxanes or sihcones. Those having a Si—OR bond are called siUcon esters. Sdoxanes and siUcon esters are discussed elsewhere ia the Eniyclopedia (see Silicon COMPOUNDS, SILICON ESTERS SILICON COMPOUNDS, SILICONES). 

Table 5 Comparison of C—X Bond Lengths for Parent Heterocycles and their Dibenzo Derivatives...

Cycloadditions including a cyclic S atom and an exocyclic C=X bond are known in the dithiazole series, e.g. as shown in Scheme 44. 

Polarographic studies on haloisoxazoles in anhydrous DMF containing R4N" were performed and the magnitude of the half-wave potentials were recorded. Cleavage of the C—X bond was faster in phenylhaloisoxazoles than in halobenzenes. Substitution patterns affected the reduction (79ZOB1322). 

For the antiaromatic three-membered heterocycles, experimental data are available only for thiirenes (and there is some doubt about the true antiaromaticity of thiirenes). Bond lengths have been calculated, however, for these antiaromatic 47r-systems (80PAC1623). In comparison with the corresponding saturated heterocycles, the C—X bond lengths are increased by 0.05 to 0.17 A and the C—C bond length is decreased by 0.2 A. 

Synthesis of heterocycles by forming C—X bonds by radical reactions is not a generally applicable method, and seems not to be useful for making small rings. However, the attack of thiol radicals on double bonds can be a practical synthetic route, such as in the conversion of 1-hexene-7-thiol to thiepane (Section 5.17.3.3.1). 

The anomeric effect is also present in acyclic systems and stabilizes conformations that allow antiperiplanar (ap) alignment of the C—X bond with a lone-pair orbital of the heteroatom. Anomeric effects are prominent in determining the conformation of acetals and a-alkoxyamines, as well as a-haloethers. MO calculations (4-3IG) have found 4kcal/mol as the difference between the two conformations shown below for methoxy-methyl chloride. ... 

These effects are attributed to differences in the c-donor character of the C—C bonds as a result of substitution. Electron-attracting groups diminish the donor capacity and promote syn addition. An alternative explanation invokes a direct electrostatic effect arising from the C-X bond dipole. 

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