Donor atom effects order

The order of donor atom effects, S- > O-, C- > N-, appears to be general for SN2 reactions with alkyl halides inasmuch as this order holds for... 

The appearance and dominance of this second-order effect can be interpreted through the strong polarization of the acceptor and donor atoms. It should also be noted that a special approach to softness matching [11,19,51] has been adapted in this study. According to this method, which was originally derived from Pearson s HSAB principle, [17] the most favorable interaction between the sites A and B... 

In listing the ways in which metal ions may promote organic reactions, the requirement that the metal ion be suitably positioned within the substrate molecule was emphasized. Specific complexation or chelation of the metal ion with the substrate appears to be an absolute requirement of metal ion catalysis. In many cases chelation appears to be the rule, which usually means that the substrate must contain a donor atom in addition to the reactive center of the molecule with which the metal ion also complexes, or must contain two donor atoms in addition to the reactive center. Many attempts have been made to correlate the effectiveness of catalysis by a series of metal ions with the relative formation constants of the complexes. Such correlations have been successful in a number of reactions, but unsuccessful in others. In the successful correlations the complex chosen for the correlation closely approximates the transition state of the reaction. This indicates that the metal ion complex must stabilize the transition state of the reaction in order to assist the reaction effectively, and that metal ion complex formation in the ground state can have an effect exactly opposite to that of catalysis, since in such a case the ground state becomes stabilized. 

The obvious deduction from these observations is that the orbital energy splitting is not primarily of a simple electrostatic nature, but reflects rather the much shorter range effects to be expected of covalence in chemical bonding to the immediate donor atoms. The conclusion is reinforced by the fact that when the known interionic separations are used together with free ion 3d-orbital wave functions to evaluate Dq for first transition series ions in an MF2 lattice, values too small by an order of magnitude are obtained.6 20-22... 

Considering the observation743 that the stabilizing effect of donor substituents decreases in the order NH2 > SH, OH > Cl, it is not surprising that examples of cations with oxygen as directly attached donor atoms, such as cation 297, are scarce.744 Cation 298 with sulfur as an intramolecular w-donor is the only example of its kind.745... 

The angular and distance information provided by the lanthanide induced shift has found widespread application from the determination of solution structures of Ln chelates [18,19] to gaining structural information on proteins, nucleotides and amino acids [19], More recently anion binding to coordinatively unsaturated lanthanide complexes has been effectively signalled as the observed lanthanide induced shift has been directly correlated to the nature of the donor atom in the axial position [8,20,21], It is the polarisability of the axial donor that ranks the second order crystal field coefficient, B02, and hence determines the magnitude of the observed shift. Values of the mean shift of the four most-shifted axial protons of the 12-Nq ring for [Yb.la]3+ are collated in Table 2. 

In the reduction of acetylene with molybdothiol and molybdoselenol complex catalysts, the effects of structural variation in ligands, variety of coordination-donor atom, kind of transition-metal ion, and other factors have been surveyed systematically. These factors have profound effects on the catalytic activity. The Mo complexes of cysteamine (or selenocysteamine), its N,N-dimethyl derivative, and its /3-dimethyl derivative give ethylene, ethane, and 1,3-butadiene, respectively, as the major product. The Co (I I) complexes of cysteine and cysteamine show higher catalytic activity than do the corresponding Mo complexes, and the order of the activity in the donor atom, namely S >Se 0 in the Co(II) complexes is consistent with that in the Mo complex systems. On the basis of electron spin resonance (ESR) features of these Mo complex catalysts, a relationship between their ESR characteristics and catalytic activities is discussed. 

In order to study the effect of hybridization of the donor atom (nitrogen) on donor strength, a complex with the isopropylideneimino donor group (7) was prepared (Eq. 4) and compared with the dimethylamino complexes 4. Compound 7 was obtained by the same exchange reaction (Eq. 1) as other hypercoordinate complexes from the isopropylideneimine 6a and 2. A crystal structure of 7 was determined, and is depicted in Fig. 6, and selected data are compared with those of the dimethylamino analog in Table IV. 

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