H Bond Formation

Fig. 8.1. Representation of transition states for the first stage of acetal hydrolysis, (a) Initial C—O bond breaking (b) concerted mechanism with C—O bond breaking leading O—H bond formation (c) concerted mechanism with proton transfer leading C—O bond breaking (d) initial proton transfer.

Fluorinated alkenes can insert into C-H bonds at elevated temperatures, a relatively unusual example of simultaneous C-C and C-H bond formation [20, 21] (equations 16 and 17)... 

The basic premise of Kamlet and Taft is that attractive solute—solvent interactions can be represented as a linear combination of a nonspecific dipolarity/polarizability effect and a specific H-bond formation effect, this latter being divisible into solute H-bond donor (HBD)-solvent H-bond acceptor (HB A) interactions and the converse possibility. To establish the dipolarity/polarizability scale, a solvent set was chosen with neither HBD nor HBA properties, and the spectral shifts of numerous solvatochromic dyes in these solvents were measured. These shifts, Av, were related to a dipolarity/polarizability parameter ir by Av = stt. The quantity ir was... 

Measurement of the properties of H-bonded systems over a range of temperatures leads to experimental values of AG, AH and AS for H-bond formation, and these data have been supplemented in recent years by increasingly reliable ab initio quantum-mechanical calculations. Some typical values for the enthalpy of dissociation of H-bonded pairs in the gas phase are in Table 3.9. 

Creating regular arrangement of nucleobases through metal ion coordination and H-bond formation 98PAC977. 

Ethylene is a simple compound of carbon and hydrogen with the formula QH4. Thus it has two less hydrogen atoms than does ethane, QH6. This means that to write a structure of ethylene we must take account of two electrons that are not used in C—H bond formation. Suppose we write an electron dot representation involving only single bonds... 

The insertion of a carbene into a Z-H bond, where Z=C, Si, is generally referred to as an insertion reaction, whereas those occurring from Z=0,N are based on ylide chemistry [75]. These processes are unique to carbene chemistry and are facilitated by dirhodium(II) catalysts in preference to all others [1, 3,4]. The mechanism of this reaction involves simultaneous Z-H bond breaking, Z-car-bene C and carbene C-H bond formation, and the dissociation of the rhodium catalyst from the original carbene center [1]. 

When C—H bond formation occurs, the result is inversion. Racemization results in polar aprotic solvents such as DMSO. In these solvents the carbanions are rela-... 

QuantlogP, developed by Quantum Pharmaceuticals, uses another quantum-chemical model to calculate the solvation energy. As in COSMO-RS, the authors do not explicitly consider water molecules but use a continuum solvation model. However, while the COSMO-RS model simpUfies solvation to interaction of molecular surfaces, the new vector-field model of polar Uquids accounts for short-range (H-bond formation) and long-range dipole-dipole interactions of target and solute molecules [40]. The application of QuantlogP to calculate log P for over 900 molecules resulted in an RMSE of 0.7 and a correlation coefficient r of 0.94 [41]. 

These two steps were chosen because they are the most activated versions of 0-0 bond scission and 0-H bond formation, respectively. There is evidence that the reactivity of other hydrogenated forms of oxygen follows a similar trend to that of atomic oxygen [Shao et al., 2007a]. 

Hydroboration is a stereospecific syn addition that occurs through a four-center TS with simultaneous bonding to boron and hydrogen. The new C—B and C—H bonds are thus both formed from the same face of the double bond. In molecular orbital terms, the addition is viewed as taking place by interaction of the filled alkene it orbital with the empty p orbital on boron, accompanied by concerted C—H bond formation.158... 

Two trials employing D2 were carried out for this system. The results demonstrate the existence of an average kinetic isotopic effect, k/H2/k/D2 = 1.27. This suggests the involvement of C-H bond formation in the rate-determining step of the mechanism. 

In biological systems one of the primary modes of molecular recognition processes occurs via H-bond formation. Research concerning design and synthesis of molecular components that can self-assemble via H-bonding interactions has been reported [90,155]. 

As remarked in Section 5.1.2, the discovery of hydrogen bonding provoked ongoing controversy between proponents of a partial covalency and advocates of an electrostatic picture of H-bond formation. The former group emphasized the importance of resonance-type chemical forces of quantum-mechanical origin that could be represented as... 

Let us examine the balance between steric and donor-acceptor forces in greater detail for the case of HF- HF. The graph below plots the adiabatic potential-energy curve for H-bond formation (solid line, circles), as well as the steric repulsion energy37 (dotted line)... 

In this case, the principal resonance delocalization accompanying H-bond formation involves only the two alternative forms of the terminal carboxylate moiety,... 

In contrast, resonance delocalization and bond alternation in the C—C=C—C backbone are only slightly affected by H-bond formation (namely, the C4—C5 bond order varies by only 0.008 between H-bonded and open conformers), because such resonance shifts do not intrinsically alter the charge distribution in the H-bonded O- H—O triad. This example illustrates the principle that H-bonding is not generally coupled to resonance per se, but only to such resonance as leads to effective CAHB enhancement (Section 5.2.2). 

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