Bonds, chemical, between transition

The rate of reaction of a series of nucleophiles with a single substrate is related to the basicity when the nucleophilic atom is the same and the nucleophiles are closely related in chemical type. Thus, although the rates parallel the basicities of anilines (Tables VII and VIII) as a class and of pyridine bases (Tables VII and VIII) as a class, the less basic anilines are much more reactive. This difference in reactivity is based on a lower energy of activation as is the reactivity sequence piperidine > ammonia > aniline. Further relationships among the nucleophiles found in this work are morpholine vs. piperidine (Table III) methoxide vs. 4-nitrophenoxide (Table II) and alkoxides vs. piperidine (Tables II, III, and VIII). Hydrogen bonding in the transition state and acid catalysis increase the rates of reaction of anilines. Reaction rates of the pyridine bases are decreased by steric hindrance between their alpha hydrogens and the substituents or... 

A question which has been keenly argued for a number of years is the following if it were possible continuously to vary one or more of the parameters determining the nature of a system such as a molecule or a crystal, say the effective nuclear charges, then would the transition from one extreme bond type to another take place continuously, or would it show discontinuities For example, are there possible all intermediate bond types between the pure ionic bond and the pure electron-pair bond With the development of our knowledge of the nature of the chemical bond it has become evident that this question and others like it cannot be answered categorically. It is necessary to define the terms used and to indicate the point of view adopted and then it may turn out, as with this question, that no statement of universal application can be made. 

Linus Pauling, "The Nature of the Chemical Bond. III. The Transition from One Extreme Bond Type to Another," JACS 54 (1932) 981003 Linus Pauling, "Interatomic Distances in Covalent Molecules and Resonance between Two or More Lewis Electronic Structures," Proc.NAS 18 (1932) 293297 Linus Pauling, "The Calculation of Matrix Element for the Lewis Electronic Structure of Molecules,"... 

Jenner [275] has presented a thorough description of several possible contributions to both the intrinsic and the environmental parts of the activation volumes, based on accurate experimental observation of pressure effect on reactions in solutions. The intrinsic contribution to the activation volume essentially derives from the differences in structure between the transition state and the reacting species, so it is directly related to the partial cleavage and formation of chemical bonds in the transition state. In cases where the environmental contribution is negligible, the activation volume variation gives a direct insight in the molecular mechanism [275, 280]. In this case in fact, considering... 

V. Chemical Bonds between Transition Metal Atoms and Ligating... 

The two glass transitions became evident due to the severing of the ester bonds formed between the polyamic acid and the epoxy upon the cyclization of the polyimide at higher cure temperatures. The PI molecules then had no direct chemical... 

One of the most interesting aspects of energy transport is the excitation percolation transition (, and its similarity (10) to magnetic phase transitions and other critical phenomena (, 8). In its simplest form the problem is one of connectivity. In a binary system, made only of hosts and donors, the question is can the excitation travel from one side of the material to the other The implicit assumption is that there are excitation-transfer-bonds only between two donors that are "close enough", where "close enough" has a practical aspect (e.g. defined by the excitation transfer probability or time). Obviously, if there is a succession of excitation-bonds from one edge of the material to the other, one has "percolation", i.e. a connected chain of donors forming an excitation conduit. We note that the excitation-bonds seldom correspond to real chemical bonds rather more often they correspond to van-der-Walls type bonds and most often they correspond to a dipole-dipole or equivalent quantum-mechanical interaction. 

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