Donor-acceptor complex Charge-transfer complexes

Type of sorbate and adsorbent in chromatography Disper- sive inter- actions Electro- static induced inter- actions Electro- XT inter- actions Donor- acceptor complex (charge- transfer complex)... 

Comparison of the PES spectral dependence with the absorption spectrum of the ms evidences that PES in the visible region is due to the formation of weak electronic Donor Acceptor (DA) Charge Transfer Complexes (CTC) with absorption maxima in the region of 400600 nm [44]. The maxima and band absorption edge of the CTC... 

The ability of compounds with double bonds to act both as electron donors and as electron acceptors in charge transfer complex formation is well known (81,82). Hammond (83) has studied the correlations of association constants and of the energy of the charge transfer absorption of 2-substituted-l,4-benzoquinones complexed with hexamethylbenzene with the Hammett equation. Charton (84) has studied the correlation with eq. (2) of association constants of 1-substituted propenes with Ag. ... 

When the intermolecular forces are relatively strong and directional, crystalline molecular compounds (crystalline molecular complexes) are formed. They have fixed stoichiometries and ordered structures. These two-component molecular crystals are also called cocrystals or maybe adduct crystals. Hydrogen-bonded cocrystals, donor-acceptor crystals (charge transfer crystals), and inclusion crystals (host-guest crystals) are examples of crystalline molecular complexes. Crystalline organic salt is a special case of hydrogen-bonded cocrystal or donor-acceptor crystal, i.e., proton (or electron) transfer from the acid (or donor) to base (or acceptor) occurred. 

The structure of the complex of (S)-tryptophan-derived oxazaborolidine 4 and methacrolein has been investigated in detail by use of H, B and NMR [6b. The proximity of the coordinated aldehyde and indole subunit in the complex is suggested by the appearance of a bright orange color at 210 K, caused by formation of a charge-transfer complex between the 7t-donor indole ring and the acceptor aldehyde. The intermediate is thought to be as shown in Fig. 1.2, in which the s-cis conformer is the reactive one. 

Zollinger and coworkers (Nakazumi et al., 1983) therefore supposed that the diazonium ion and the crown ether are in a rapid equilibrium with two complexes as in Scheme 11-2. One of these is the charge-transfer complex (CT), whose stability is based on the interaction between the acceptor (ArNj) and donor components (Crown). The acceptor center of the diazonium ion is either the (3-nitrogen atom or the combined 7r-electron system of the aryl part and the diazonio group, while the donor centers are one or more of the ether oxygen atoms. The other partner in the equilibrium is the insertion complex (IC), as shown in structure 11.5. Scheme 11-2 is intended to leave the question open as to whether the CT and IC complexes are formed competitively or consecutively from the components. ... 

As we have seen from reaction 4.49 donor-acceptor complexes (Lewis- or 7r-type) occur in a fairly inert medium (such as cyclohexane) via charge transfer between a base (electron donor) and an acid (electron acceptor by its electron deficiency). In a few instances, e.g., in the Bonitz titration29 of the precatalyst diethylalaminium chloride with isoquinoline, the complex constists of an ion-pair ionizate. 

Mulliken [3] presented a classification of electron donor-acceptor complexes based on the extent of intermolecular charge transfer that accompanies complex formation. An outer complex is one in which the intermolecular interaction B- XY is weak and there is little intra- or intermolecular electric charge redistribution, while an inner complex is one in which there is extensive electric charge (electrons or nuclei) redistribution to give [BX] + - -Y . Inner complexes are presumably more strongly bound in general than outer complexes. 

It is important to recognize that the intermolecular long-distance bonding with the participation of halogen derivatives represents a specific example of the broad general area of donor/acceptor interactions. Moreover, the complexes of molecular iodine, bromine and chlorine with aromatic donors represent classic examples of charge-transfer compounds [26-28] that are vital for the development of Mulliken theory of intermolecular association [29-31]. The latter thus provides the convenient framework for the... 

The donor-acceptor complexes [Ir(/r-dmpz)(CO)(PPh2 0(CH2)2R )]2 exhibit photo-induced electron-transfer rate constants of 1012s—1 and charge recombination rates slower than 2 x 10los-1 when R = pyridine and 4-phenylpyridine.534 Further studies on these complexes revealed that recombination reactions were temperature dependent and slower for the deuterated acceptors.535... 

Molecules of this type are often called donor-acceptor complexes or sometimes charge transfer complexes (because charge is transferred from the donor to the acceptor as the nonbonding electron pair of the donor atom is shared with the acceptor atom). In other words, there is a formal transfer of one electron, which is evident in the formal charges on the atoms in the complex. Once formed, however, the bond is simply a covalent bond consisting of a pair of shared electrons, whose origin is irrelevant to the nature of the... 

The scope of the Patemo-Buchi cycloaddition has been widely expanded for the oxetane synthesis from enone and quinone acceptors with a variety of olefins, stilbenes, acetylenes, etc. For example, an intense dark-red solution is obtained from an equimolar solution of tetrachlorobenzoquinone (CA) and stilbene owing to the spontaneous formation of 1 1 electron donor/acceptor complexes.55 A selective photoirradiation of either the charge-transfer absorption band of the [D, A] complex or the specific irradiation of the carbonyl acceptor (i.e., CA) leads to the formation of the same oxetane regioisomers in identical molar ratios56 (equation 27). 

Benzpinacols (or their trimethylsilyl ethers) are effective electron donors and readily form vividly colored charge-transfer complexes with common electron acceptors such as chloranil (CA), dichlorodicyanobenzoquinone (DDQ), tetracyanobenzene (TCNB), methyl viologen (MV2+), and nitrosonium (NO+) cation.191-194 For example, the exposure of a silylated benzpinacol to chloranil... 

A variety of other highly-strained electron-rich donors also form colored complexes (similar to homobenzvalene) with various electron acceptors, which readily undergo thermal cycloadditions (with concomitant bleaching of the color).209 For example, Tsuji et al.210 reported that dispiro[2.2.2.2]deca-4,9-diene (DDD), with an unusually low ionization potential of 7.5 eV,211 readily forms a colored charge-transfer complex with tetracyanoquinodimethane (TCNQ). The [DDD, TCNQ] charge-transfer complex undergoes a thermal cycloaddition to [3,3]paracyclophane in excellent yield, i.e.,... 

The general concept of a charge-transfer complex was introduced by Mulliken77 to describe a form of association between donor (D) and acceptor (A) molecules that could be represented in resonance language as... 

Let us briefly mention some other binary A- B charge-transfer complexes involving neutral monomers A and B chosen rather arbitrarily from the large number of possible species of this type. These examples serve to illustrate interesting aspects of the general CT phenomenon and exhibit the strong commonality with donor-acceptor interactions considered elsewhere in this book. 

At shorter distances, particularly those characteristic of H-bonded and other charge-transfer complexes, the concepts of partial covalency, resonance, and chemical forces must be extended to intramolecular species. In such cases the distinction between, e.g., the covalent bond and the H-bond may become completely arbitrary. The concept of supramolecular clusters as fundamental chemical units presents challenges both to theory and to standard methods of structural characterization. Fortunately, the quantal theory of donor-acceptor interactions follows parallel lines for intramolecular and intermolecular cases, allowing seamless description of molecular and supramolecular bonding in a unified conceptual framework. In this sense, supramolecular aggregation under ambient thermal conditions should be considered a true chemical phenomenon. 

Mulliken s general concept of charge-transfer complexes can be given explicit and quantitative reformulation in the NBO framework. This allows one to recognize the essential electronic continuity that relates CT complexes of different types, including H-bonded species (n-a CT complexes). Particular attention was paid to the interesting 7t-7t CT complexes of NO+ and related pi-acids, which exemplify the distinctive quantal dependence on the shapes of donor and acceptor orbitals. 

---