Acceptor triple

Stracke, A. Wendorff, J. H. Janietz, D. Mahlstedt, S. (1999). Functionalized Liquid-Crystalline Donor-Acceptor Triple Compounds Containing Azobenzene for Optical Storage. Ado. Mater. 1999,11,667-670. 

A gap level is called an acceptor level if tlie defect is neutral when tlie state is empty (no electron). It is called a donor level if tlie defect is neutral when tlie state is occupied (one electron). The foniier is often labelled (0 / -) and tlie latter (-t / 0), where tlie first (second) sign refers to tlie charge of tlie defect when no electron (one electron) is present. Double or triple acceptor and donor levels are similarly labelled. 

It was assumed that the failure of cyclization of 3-amino- and 5-amino-4-acetylenylpyrazole derivatives is due both to the decreased nucleophilicity of the amino groups in the acceptor positions 3 and 5 of the pyrazole ring and to the low electrophilicity of the triple bond carbons in position 4 of the ring. 

The interaction between a 4-iodopyrazole-3-carboxylic acid and copper ace-tylides having both donor and acceptor substituents at the triple bond generated six- rather than five-membered lactones, as in the aromatic series (Scheme 117). 

All these compounds possess a highly electrophilic triple bond. In a number of cases the nucleophilic addition occurs at this bond only, whereas the carbonyl function acts as a negative charge acceptor. 

Much earlier information on the structure of diazonium ions than that derived from X-ray analyses (but still useful today) was obtained by infrared spectroscopy. The pioneers in the application of this technique to diazonium and diazo compounds were Le Fevre and his school, who provided the first IR evidence for the triple bonds by identifying the characteristic stretching vibration band at 2260 cm-1 (Aroney et al., 1955 see also Whetsel et al., 1956). Its frequency lies between the Raman frequency of dinitrogen (2330 cm-1, Schrotter, 1970) and the stretching vibration frequency of the C = N group in benzonitrile (2255 cm-1, Aroney et al., 1955). In substituted benzenediazonium salts the frequency of the NN stretching vibration follows Hammett op relationships. Electron donor substituents reduce the frequency, whereas acceptor substituents increase it. The 4-dimethylamino group, for example, shifts it by 103 cm-1 to 2177 cm-1 (Nuttall et al., 1961). This result supports the hypothesis that... 

Dihydro-l,2,5-thiadiboroles (Et2C2B2R2S) have remarkable acceptor properties toward metal-ligand moieties. Dihydrothiadiborole-derived complexes can be achieved thermally or photochemically, e.g., Co and Fe sandwich, triple-decked and even tetradecked complexes are known, all having direct metal-boron bonds. 

Both theoretical and experimental data (in the solid, liquid, and gas phases) prove that the tendency of halocarbons to work as XB donors decreases in the order I > Br > Cl [66-68]. Clearly, polarizability and not electronegativity plays a key role. 3-Halo-cyanoacetylene works as self-complementary module and the N X distance is beautifully consistent with the scale reported above, being 2.932, 2.978 and 2.984 A in the iodo, bromo and chloro derivatives, respectively [69,70]. The same trend is observed when a phenyl, rather than a triple bond, spaces the donor and acceptor sites. The N Br distance in 4-bromobenzonitrile is longer than in the 4-iodo derivative [71,72] and no XB is present in the chloro and fluoro analogues, wherein molecules are pinned by N H and X- H short contacts [73]. PFCs have a very poor tendency, if any, to work as XB donors [74-77] and no crystal engineering can be based on such tectons. However, F2 is a quite strong XB donor and several adducts have been described in the gas phase [11,18] (see also the chapter by Legon in this volume). 

For example, such attempts were undertaken in a body of work [60] dealing with the preparation (through acceptor-catalytic copolyesterification) of triple copolyesters composed from the residues of aromatic dicarboxylic acids, bisphenols and N-methyldielhanolamine (NMDEA). Scheme 7 illustrates the principle of such a syntheses the upper part shows the chemical... 

Germanium crystals that contain the substitutional triple acceptor copper (Hall and Racette, 1964), as well as hydrogen, exhibit in PTIS a series of broad lines that belong to an acceptor with a ground state at 17.81 meV above the top of the valence band (Haller et al., 1977a). PTIS studies over a range of temperatures have shown that this acceptor has a ls-state that is split into a large number of components that are closely spaced (Kahn et al., 1987). When thermally populated, each of the components of the ls-state manifold acts as an initial state for optical trasitions of the bound hole to one of the effective mass-like excited states. This in turn explains why the lines of this center appear broad. 

An example is the oxidation of a double positively-charged ferrous ion (chemical symbol Fe2 ) to the triple positively-charged ferric ion (Fe3 ), where one electron is donated to an external electron acceptor ... 

Cowley, A. H. From group 13-group 13 donor-acceptor bonds to triple-decker cations. Chem. Commun. 2004, 2369-2375. 

In a recent series of experiments, Suksangpanya et al. [67] have investigated the interactions between pyrimidine bases and [Cu(Lkl)]2+ cations. Amidino-O-alky-lureas contain an A-D-D sequence, similar to that of guanine. The only difference lies in the oxygen acceptor, which is part of an ether linkage in the amidino-0-alkylurea but part of a carbonyl functionality in guanine. Despite this difference, the formation of a triple complementary interaction between amidino-O-alky-lurea and cytosine, which has a D-A-A sequence was thought to be feasible. 

The reactions of the corresponding propargyl sulfoxides and sulfones now resemble the chemistry of the other acceptor-substituted derivatives such as ketones and aldehydes (see Section 1.2.4). Compared with the thioethers, here much milder bases are sufficient apart from aluminum oxide, often triethylamine or potassium carbonate are used. Sometimes even a spontaneous isomerization takes place. The selective isomerization of one triple bond in the presence of a second triple bond in 126 [313] (Scheme 1.56) or an allyl sulfone in 129 [314] (Scheme 1.57) are just two examples out of a whole series [178, 304, 313, 315-331]. When, on the other hand, the in situ oxidation of 126 was carried out in an aprotic solvent, no isomerization at all was observed. 

Remarkably, the regioselectivity of the cuprate addition to acceptor-substituted enynes is also insensitive to the steric properties of the substrate. Thus, enynes with tert-butyl substituents at the triple bond (e.g. 68) underwent 1,6-additions even when the cuprate was also sterically demanding (Scheme 2.24) [47]. The method is therefore highly suitable for the preparation of sterically encumbered allenes of type 69. 

Analogously, the trienynoate 92 reacted in a 1,10-addition to give the 3,5,7,8-tetra-enoate 93 and the even higher unsaturated allene 95 was obtained from the Michael acceptor 94 containing four double bonds between the triple bond and the acceptor substituent (Scheme 2.33). In the latter case, however, the yield was only 26% this is presumably due to the reduced thermal stability of the starting material and/or the addition product (the 1,12-adduct 95 was the only isolable reaction product, apart from polymeric compounds) [57]. 

The isomerization, itself, originates from the a complex (B in Figure 3). However the total activation energy depends critically on the relative energy of A and B (Figure 3). An alkyne C=C triple bond binds more efficiently to a transition metal complex than a o C-H bond since the % C-C orbital is a better electron-donor and the 71 C-C orbital a better electron acceptor than the a and a C-H orbitals, respectively. However, the difference in energy between the two isomers is relatively low for a d6 metal center because four-electron repulsion between an occupied metal d orbital and the other n C-C orbital destabilizes the alkyne complex. This contributes to facilitate the transformation for the Ru11 system studied by Wakatsuki et al. 

The same dichotomy of bonding models is also found for carbyne complexes that have a formal triple bond M=CR. There are metal-carbyne bonds that belong to the donor-acceptor type (the Fischer car-... 

Similar schemes can be developed easily for analogous reactions of acceptor-substituted polyenes. For example, a triene with an acceptor group in 1-position can form six regioi-someric products of Michael addition and electrophilic capture, and each of these exists as E/Z stereoisomers, diastereomers and/or enantiomers. Thus, reactions of this type are only useful if both the regio- and stereoselectivity can be controlled fortunately, only one isomeric Michael adduct is formed in many cases. This is true in particular for polyunsaturated Michael acceptors which bear at least one triple bond besides one or more double bonds. An additional feature of the latter substrate type is that nucleophilic additions can... 

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