Covalent bond stretching

Table 5.5. Hydrogen-bond energies A b-h< HF monomer net charge 2hf< H-bond lengths - und covalent-bond stretchings A R/ for CO- -HF and OC- -HF isomers (see Fig. 5.3)...

Table 5.7. Hydrogen-bond energies Aiso-H. bond lengths Ro w and Rah, covalent-bond stretching A7 ah, andfrequency change AvM for F O- -HA...

The term representing the covalent bond-stretching interaction reads... 

A covalent bond (or particular nomial mode) in the van der Waals molecule (e.g. the I2 bond in l2-He) can be selectively excited, and what is usually observed experimentally is that the unimolecular dissociation rate constant is orders of magnitude smaller than the RRKM prediction. This is thought to result from weak coupling between the excited high-frequency intramolecular mode and the low-frequency van der Waals intemiolecular modes [83]. This coupling may be highly mode specific. Exciting the two different HE stretch modes in the (HF)2 dimer with one quantum results in lifetimes which differ by a factor of 24 [84]. Other van der Waals molecules studied include (NO)2 [85], NO-HF [ ], and (C2i J )2 [87]. 

This is because rubber, like many polymers, is composed of long spaghetti-like chains of carbon atoms, all tangled together as we showed in Chapter 5. In the case of rubber, the chains are also lightly cross-linked, as shown in Fig. 5.10. There are covalent bonds along the carbon chain, and where there are occasional cross-links. These are very stiff, but they contribute very little to the overall modulus because when you load the structure it is the flabby Van der Waals bonds between the chains which stretch, and it is these which determine the modulus. 

Fig. 23.2. A schematic of o linear-amorphous polymer, showing the strong covalent bonds (full lines) and the weak secondary bonds (dotted lines). When the polymer is loaded below Tg, it is the secondary bonds which stretch.

The difficulty of assigning a formal oxidation state is more acutely seen in the case of 5-coordinate NO adducts of the type [Co(NO)(salen)]. These are effectively diamagnetic and so have no unpaired electrons. They may therefore be formulated either as Co -NO or Co -NO+. The infrared absorptions ascribed to the N-O stretch lie in the range 1624-1724 cm which is at the lower end of the range said to be characteristic of NO+. But, as in all such cases which are really concerned with the differing polarities of covalent bonds, such formalism should not be taken literally. 

As the most notable contribution of ab initio studies, it was revealed that the different modes of molecular deformation (i.e. bond stretching, valence angle bending and internal rotation) are excited simultaneously and not sequentially at different levels of stress. Intuitive arguments, implied by molecular mechanics and other semi-empirical procedures, lead to the erroneous assumption that the relative extent of deformation under stress of covalent bonds, valence angles and internal rotation angles (Ar A0 AO) should be inversely proportional to the relative stiffness of the deformation modes which, for a typical polyolefin, are 100 10 1 [15]. A completly different picture emerged from the Hartree-Fock calculations where the determined values of Ar A0 AO actually vary in the ratio of 1 2.4 9 [91]. 

The short lifetimes of carbon-centered monoradicals are generally reduced in the case of diradicals due to their propensity to form covalent bonds. It has been suggested that stable diradicals may be observable from highly strained bicyclic molecules where the TS for inversion is a diradical. Unfortunately, only persistent diradicals have been obtained in this way. Akin to this approach, in a recent attempt to generate the oxyallyl diradical, Sorensen and co-workers synthesized two substituted bicyclobutanones hoping to stretch and homolytically break the central bond using bulky substituents, which would also stabilize the diradical. Though the bicyclobutanones did not yield the desired oxyallyl derivative, the X-ray structures showed... 

Chain stretching is governed by the covalent bonds in the chain and is therefore considered a purely elastic deformation, whereas the intermolecular secondary bonds govern the shear deformation. Hence, the time or frequency dependency of the tensile properties of a polymer fibre can be represented by introducing the time- or frequency-dependent internal shear modulus g(t) or g(v). According to the continuous chain model the fibre modulus is given by the formula... 

Over the past decade a number of new covalently bonded TTF/ferrocene adducts have been reported [77, 78]. The crystal structure of the l,l -bis(l,3-dithiole-2-ylidine)-substituted ferrocene derivative has been published [77]. In this complex, ferrocene has essentially been incorporated as a molecular spacer between the two l,3-dithole-2-ylidene rings forming a stretched TTF molecule. This adduct, and its methyl-substituted derivative, have been combined with TCNQ to form charge-transfer complexes with room temperature powder conductivities of 0.2 S cm-1. Similar diferrocenyl complexes have been prepared with bis (dithiolene) metal complexes [79, 80]. 

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