Inductive effect, definition

As the data for the above two complexes indicate, there exists a definite correlation of the redox potentials with substituent inductive effects. This is further illustrated in a plot of the potentials for all the Mn(III)(R2Dtc)3/ Mn(IV)(R2Dtc)3 couples versus the potentials of the Mn(II)(R2Dtc)3/ Mn(IIlXR2 Dtc)3 couples. The plot is very nearly linear, with a slope A/(recl/ AZTox = 1.1, and clearly indicates that substituents that stabilize Mn(IV) destabilize Mn(II) and vice versa. 

The absence of such an effect has been definitely excluded by Rappoport and Apeloig (1970) by the observation that the two geometric isomers 143 and 144 react at virtually the same rate in ethanol-water 4 1 and acetic acid at 120° as well as in formic acid-acetic acid 1 1 at 99-7°. Moreover, the rate of 143 and 144 is intermediate between that of 141 and 142, as expected for the additivity of purely inductive effects. 

Despite the success in parameterizing acid/base and many other properties for a range of different compounds, it is obvious that the simple electrostatic model used by Taft and extended by others [27, 28] have fundamental weaknesses - both with regards to the domain of validity and at a more fundamental level. The model is more intuitive than physical, in the sense that the inductive effect, polarisation effect, resonance effect, mesomeric effect and steric effect have no proper quantum mechanical definition, and can therefore not be derived directly from the system s wave function [29,30]. 

The determination of the crystal structures of a series of silyl(amino)boranes shows that the B-Si bond is significantly shortened by the introduction of chlorine substituent at boron and is even Shorter in the presence of a Q atom at the silyl group. This definitely shows that the Cl atoms have a noticeable inductive effect on the length (and strength) of the B-Si single bond. 

Requirement of synchronous asymmetric inductions (RSAI) All coordination modes favor transition states with equally directed asymmetric inductions (strong definition). The cases of synchronous asymmetric inductions/preferred asymmetric induction/zero total stereoselectivity have been corroborated mathematically for ligands with two coordination modes [7]. If there are more than two coordination modes, the RSAI is already valid if at least the two most stabilized transition states have synchronous asymmetric inductions (weak definition). The advantage of the RSAI is that a high total stereoselectivity can be predicted independently of solvent effects. Any antagonism... 

The structure of Eq. (6.2) clearly shows that the effect of the next-nearest neighbors on the a value of a given atom is proportional to the corresponding a through a quantity of the second order in the y s, as should be expected of inductive effects according to the chemical definition. 

Multiple exposure studies may include obtaining information on possible enzymatic inhibition or induction effects as well as the possibility of bioaccumulation. In such studies, animals are dosed by gavage (or other appropriate route) for 14 days with one dose, usually the highest anticipated dose sufficient animals are used so that three data points are available at each blood sampling time. Blood samples are taken at multiple time points after dosing and analyzed for test chemical or metabolite. These results are compared to the results of the single- exposure definitive study to determine possible enzymatic inhibition or induction effects and bioaccumulation of the test chemical. 

Hammett a values are adequate for reactions and equilibria involving separation of substituent and reaction centre by a phenylene grouping. Examination of aliphatic species necessitates a more sophisticated set of o values as transmission effects are now markedly different from the model. Resonance and inductive effects may be separated if we can use as models reactions with no resonance interactions so that a° type values may be defined. Entirely new approaches have led to the definition of an inductive scale of a parameters (O]). Although some of these parameters are now only of historic value we shall include a brief discussion of early attempts to define the a, scale. 

---