Let us consider the general trends of the reactivity of C-C, C-S, and C-Q (Q = Cl, Br, I) bonds towards oxidative addition and reductive elimination (Scheme 7-25). In many cases, either C-C bond-forming reductive elimination from a metal center (a) or the oxidative addition of a C-Q bond to a low-valent metal center is a thermodynamically favorable process (c). On the other hand, the thermodynamics of the C-S bond oxidative addition and reductive elimination (b) lies in between these two cases. In other words, one could more easily control the reaction course by the modulation of metal, ligand, and reactant Further progress for better understanding of S-X bond activation will be achieved by thorough stoichiometric investigations and computational studies. [Pg.248]

Scheme 7-25 General trend of reactivity of C-C, C-S, and C-Q Bonds toward M (a) favored reductive elimination, (b) adjustable by metal, ligands and reactand, (c) favored oxidative addition... |

As can be seen from the mean absolute deviations from experiment, all levels of theory give good overall performance for bond lengths. The poorest result for most of the theoretical procedures is observed for the O-Q bond length in 0C1, which is overestimated (by 0.023 - 0.061 A) by all the methods listed in Tables 6.2 and 6.3. This appears to be a consequence of basis set deficiencies, with improved geometries being obtained at all levels of theory with larger basis sets [28], The OCl radical has therefore been excluded from the statistical analysis of the results. [Pg.167]

A. Partial Derivatives and Polarizability Coefficients Expansion of (8) yields a polynomial, the characteristic or secular polynomial, whose roots are determined by the values of the parameters , vw- The ground state energy (12) is likewise a function of the (a,j3) parameter values, as are all quantities such as AO coefficients in the MO s, charges q bond orders p t, etc. It is possible, therefore, to specify the h partial derivative with respect to any or at an arbitrary point defined by a set of values (a,j8) in the parameter space, and to make expansions such as... [Pg.89]

Figure 6, Reactivity space having bond polarity, Q, bond dissociation energy, BDE, and resonance effect parameter, R, as coordinates ... |

Table 3 P-NMR data, M-P bond lengths, and M-P-Q bond angles of representative phosphinidene complexes ... |

The energy Ae required to stretch the H+-H Q bond to the critical condition for electron tunneling is a fraction of the energy gap Ac0, which must be closed to make... [Pg.810]

The sum of all these factors for a specific problem is equal to the trace of the matrix of the corresponding characteristic problem4 the sum of their squares equals the sum of the squares of all matrix elements of the corresponding characteristic problem.64 These relations are useful for checking the values of orbital energies. By an equally simple procedure1-4 the values of expansion coefficients yield the values of ir-electron densities (q), bond orders (p), and free valences (F) these quantities are usually presented in the form of a molecular diagram ... [Pg.5]

Recently, a series of models of 16 polynuclear pyridine-like heterocycles (Fig. 9 shows formulas of eleven of these) were treated using the HMO approximation7 (SN = 0.6, inductive effect not allowed for) and the following reactivity indices calculated 77-electron densities (q), bond orders (p), free valences (F, N x = Wheland s atom localization energies (A(,Ar,An), and superdelocalizabilities, both exact (Se,Sr,Sn) and approximate (S e,S r,S n). Atom-atom polarizabilities150 (773) had been calculated earlier.151 Some of the indices calculated are presented in Section VI, B. [Pg.99]

Much coordination chemistry has been carried out with simple pyrimidines and the nucleic acid bases. The crystal structure566 of tetrakis(l-methyl-pyrimidine-2-thione)zinc(II) perchlorate bis(propanone) demonstrates unidentate coordination by the non-methylated (N-3) nitrogen atom, with r(Zn—N) at 2.058 and 2.060 A. The structure of dichlorobis(l-methylcytosine)cadraium(II)567 involves two Cd—Q bonds (2.497 and 2.485 A) and two Cd—N(3) bonds (2.281 and 2.296 A) with approximately tetrahedral stereochemistry. [Pg.957]

Two atoms, p and q, bonded together at a distance rpq give a contribution, ipq(s), to the diffraction curve, which can be calculated according to the Debye expression... [Pg.168]

Despite this better mode of strain dissipation in the Ct—Ct series the central C—C bond length in 2,3-dimethylbutane, the parent compound, is shorter than the extrapolated bond length of a hypothetical strainless parent Cq—Cq compound 79). This supports the proposal made before, that Q—Q bonds are intrinsically stronger than Cq—Cq bonds. If the difference in resonance stabilization of tertiary and secondary alkyl radicals was the dominating factor determining these bond strengths it should have no consequences for the bond lengths801. [Pg.18]

Carbon-13 chemical shifts are typically 75, 106, 128.5 and 86 for, respectively, a, o, m and p carbons indicating delocalized anions within contact ion-pairs. At low temperature, all the ring hydrogens are nonequivalent and, with increasing temperature, the resonances for the two ortho protons average as do those for the meta protons due to increasingly faster rotation around the Ca—Q bonds. The e(ae) elements which account for the changes in the proton NMR line shape analysis are described in equation 27. [Pg.39]

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