Silylenes properties

For copolymers of structure I, for both types of side-chains, there is a striking similarity with the optical properties of the corresponding models the absorption and photoluminescence maxima of the polymers arc only 0.08-0.09 eV red-shifted relative to those of the models, as shown in Figure 16-9 (left) for the octyloxy-substituted compounds. The small shift can be readily explained by the fact that in the copolymers the chromophorcs are actually substituted by silylene units, which have a weakly electron-donating character. The shifts between absorption and luminescence maxima are exactly the same for polymers and models and the width of the emission bands is almost identical. The quantum yields are only slightly reduced in the polymers. These results confirm that the active chro-mophores are the PPV-type blocks and that the silylene unit is an efficient re-conjugation interrupter. 

Polysilanes with alkoxy groups are more light sensitive than conventional polysilanes. They degrade rapidly in the presence of light in agreement with the facile formation of silylene from dialkoxydisilanes. Properties of these polymers are currently being investigated. 

The discovery that soluble high molecular weight polysilanes may be prepared by the reductive coupling of dichlorodialkylsilanes by alkali metals (1,2) has led to considerable work on the properties of this interesting class of polymers (3,4,5). The preparation of the polymers leaves much to be desired as frequently the high polymer is only a minor product. Mechanistic studies of the reaction with a view to improving the relevant yields have been few (6). The major ones by Zeigler (7,8,9) showed that a silylene diradical was not involved in the reaction, and stressed the importance of polymer solvent interactions. 

It has become common to classify all molecular compounds, which fulfill the above characteristics, as carbene analogs 9,13>. As a consequence, compounds of divalent silicon, germanium, tin, and lead may be regarded as carbene-like and are therefore called silylenes, germylenes, stannylenes, and plumbylenes. In contrast to carbenes they have one property in common the energetically most favorable electronic state is the singlet 1a2 found by experiments and calculations 9). 

The stability of molecules depends in the first place on limiting conditions. Small, mostly triatomic silylenes and germylenes have been synthesized successfully at high temperatures and low pressures, 718). Their reactions can be studied by warming up the frozen cocondensates with an appropriate reactant, whereas their structures are determined by matrix techniques 17,18). In addition, reactions in the gas phase or electron diffraction are valuable tools for elucidating the structures and properties of these compounds. In synthetic chemistry, adequate precursors are often used to produce intermediates which spontaneously react with trapping reagents 7). The analysis of the products is then utilized to define more accurately the structure of the intermediate. 

A much explored pathway to simple silenes involves the thermolysis of silacyclobutanes at 400-700°C, the original Gusel nikov-Flowers (155) route. Such temperatures are not readily conducive to the isolation and study of reactive species such as silenes except under special conditions, and flash thermolysis, or low pressure thermolysis, coupled with use of liquid nitrogen or argon traps has frequently been employed if study of the physical properties is desired. Under these high temperature conditions rearrangements of simple silenes to the isomeric silylenes have been observed which can lead to complications in the interpretation of results (53,65). Occasionally phenyl-substituted silacyclobutanes have been photolyzed at 254 nm to yield silenes (113) as has dimethylsilacyclobutane in the vapor phase (147 nm) (162). 

The ability to insert in many element-element bonds is an important property of 1 the r -p1 rearrangement of the pentamethylcyclopentadienyl ligands during the reaction is a prerequisite to show a silylene-type reactivity. From a preparative point of view it is worth mentioning that element-silicon bonds which otherwise are difficult to form are easily accessible with the help of 1. In addition, the leaving group character of the pentamethylcyclopentadienyl substituents allows further chemical transformations (vide infra). 

A varied and productive chemistry is now established for most of the Group IV dihalides. By combining high temperature and low temperature techniques, one may isolate AX2 species and observe molecular parameters as well as physical and chemical properties. The CX2 (carbenes) and SiX2 (silylenes) molecules have a rich chemistry and provide new and unique opportunities for organic and organo-metallic syntheses. 

Besides the applications of the electrophilicity index mentioned in the review article [40], following recent applications and developments have been observed, including relationship between basicity and nucleophilicity [64], 3D-quantitative structure activity analysis [65], Quantitative Structure-Toxicity Relationship (QSTR) [66], redox potential [67,68], Woodward-Hoffmann rules [69], Michael-type reactions [70], Sn2 reactions [71], multiphilic descriptions [72], etc. Molecular systems include silylenes [73], heterocyclohexanones [74], pyrido-di-indoles [65], bipyridine [75], aromatic and heterocyclic sulfonamides [76], substituted nitrenes and phosphi-nidenes [77], first-row transition metal ions [67], triruthenium ring core structures [78], benzhydryl derivatives [79], multivalent superatoms [80], nitrobenzodifuroxan [70], dialkylpyridinium ions [81], dioxins [82], arsenosugars and thioarsenicals [83], dynamic properties of clusters and nanostructures [84], porphyrin compounds [85-87], and so on. 

However, another study concluded that the changes of the hydrogen-bond stability may be important in biological processes. For these, the influence of local electric fields created by Li+, Na+, and Mg2+ ions on the properties and reactivity of hydrogen bonds in HF and HC1 dimer has been carried out by means of ab initio self-consistent field (SCF) method [33]. A few years later, the effect of intensity and vector direction of the external electric field on activation barriers of unimole-cular reactions were studied using the semiempirical MINDO/3 method [34]. However, both semiempirical and ab initio calculations were performed to study the multiplicity change for carbene-like systems in external electric fields of different configurations (carbene and silylene) and the factor that determines the multiplicity and hence the reactivity of carbene-like structures is the nonuniformity of the field [35]. 

Linear polycarbosilanes and polycarbosiloxanes-especially those containing arylene units in the chain-have specific physico-chemical properties which can be applicable in heat-resistant materials [29-31]. Phenylene-silylene-ethylene-polymers, which may serve as potential substrates for applications as membrane materials are usually obtained in the presence of platinum catalysts [32], although other transihon-metal complexes have also been tested in this process. 

Several examples of carbenoid ion-radicals are discussed within this book. A silylene anion-radical preparation and properties is exemplified here. Scheme 2.5 shows the path to this species. Tetrakis(di-tert-butytmethylsilyl)disilylene was reduced by lithium or sodium salt of naphthalene anion-radical in THF at 78°C and then 12-crown-4 was added to the resulting reaction mixture. The silylene anion-radical was obtained as the corresponding alkali salt. Red crystals of the salt were isolated and characterized by ESR spectroscopy and x-ray crystallography (Inoue et al. 2007). 

E = Si) and EN(R)CH=CHNR (e.g. 2, E = Si) (R = H, Bu ) have been reported " " it was concluded that there is significant p -p -delocalisation for the latter compounds. The relationship between stability, acid-base and spin properties, nucleophilicity and electrophilicity in a series of silylenes was studied by conceptual density functional theory." ... 

III. Spectroscopic Properties of Silylene-Lewis Base Adducts. 11... 

Silylenes are, in a certain sense, the younger but bigger siblings of car-benes, and their chemistry has been reviewed several times.1 In 1978, Gaspar asked the question Are we to conclude from our present knowledge that nature has designed silylenes to humbly mimic carbenes, or is the situation different 13 Today, we know that silylenes and carbenes have a number of properties in common, but also show significant differences. 

SPECTROSCOPIC PROPERTIES OF SILYLENE-LEWIS BASE ADDUCTS... 

The only exception to these uniform spectroscopic properties of silylene-Lewis base complexes, i.e., the hypsochromic shift on complexation, is silacarbonyl ylide 27, the absorption maximum of which is shifted to wavelengths longer than that of free dimesitylsilylene (20a) 31 an explanation of this observation is yet to come. 

Spectroscopic Properties of Silylene-Lewis Base Adducts. 

An organosilicon compound (tetramesityldisilene) containing a silicon to silicon double bond has been synthesized. It is a crystalline solid, mp 176C, and has reactive properties similar to olefins. Compounds of the type are silylenes. 

The effect of substituents on the properties and structure of silylenes was analyzed in detail by Apeloig and Karni on the basis of ab initio calculations137. 

TABLE 2. Spectroscopic properties of silylene-isocycanide complexes... 

The properties of the stable silylenes raise interesting questions of chemical bonding, many of which apply also to the carbenes, 58a-f. First, why are these compounds so stable compared to ordinary silylenes (carbenes) Steric hindrance may be a factor, but it is unlikely to be a major one silylenes far more hindered than 59-63 dimerize at low temperatures, as was described in Section III.C181. 

To date, chemical properties have been reported mainly for 59 and 61. Occupancy of the silicon 3p orbital by electrons from nitrogen greatly reduces the electrophilicity of these silylenes. This, together with probable aromatic stabilization, significantly mutes the behavior of 59 and 61 as silylenes. For example, 59 does not insert into Si—H bonds, or react with alkynes such as PhC=CPh367, Moreover, 59 shows no Lewis acidic behavior, even toward bases as strong as pyridine. 

In 1981, West et al. synthesized the first stable disilene 1 via the dimerization of the corresponding silylene generated by the photolysis of a trisilane and characterized the structure by conventional spectroscopies [Eq. (2)].5 Availability of 1 and other stable disilenes has stimulated theoretical and experimental studies of various aspects of disilenes such as their bonding and structure, spectroscopic properties, reactivities, applications to the synthesis of novel types of organosilicon compounds, etc. 

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