Silicon nitrogen-sulfur bonds

As mentioned in this chapter, in recent years much progress has been made in the chemistry of silicon-chalcogen multiple bonds. For silicon-sulfur doubly-bonded compounds, we have now several isolated examples, both kinetically stabilized and thermodynamically stabilized. Furthermore, there have been reports of the synthesis and characterization of stable compounds with silicon-nitrogen double bonds (i.e. silanimines or iminosilanes) as well as their heavier group 15 element analogues such as phosphasilenes and arsasilenes. 

You have now seen how enols and enolates react with electrophiles based on hydrogen (deuterium), carbon, halogens, silicon, sulfur, and nitrogen. What remains to be seen is how new carbon-carbon bonds can be formed with alkyl halides and carbonyl compounds in their normal electrophilic mode. These reactions are the subject of Chapters 26-29. We must first look at the ways aromatic compounds react with electrophiles. You will see similarities with the behaviour of enols. 

The class of phosphaalkenes with isolated P=C double bonds was first synthes ized by Becker.33 His synthetic strategy starting from trimethylsilylphosphines and acyl chlorides is still the most versatile (Protocol 3). The principle is based on the easily achievable, 1,3-silatropic migration of a silyl group bonded to phosphorus to a doubly bonded element such as nitrogen, oxygen, or sulfur. The process is favoured energetically by the construction of the P=C double bond with concomitant formation of a very stable silicon-element bond. 

While organometallic reagents condense with N-substituted imines (Schiff bases) to afford, after hydrolysis, good yields of substituted amines, the reaction with N-unsubstituted imines (203) derived from ammonia (which are easily hydrolyzed and self condense) is not synthetically useful. As a result, the use of masked imines containing labile silicon- or sulfur-nitrogen bonds, such as N-trimethylsilyl-imines (204) or N-sulfenimines (205), has been explored. 

Often, most atoms are bonded to a single atom. This atom is called the central atom. Hydrogen and the halogens are very rarely, if ever, centr2d atoms. Carbon, silicon, nitrogen, phosphorus, oxygen, and sulfur are always good candidates, because they form more than one covalent... 

In an attempt to stabilize low-valent silicon compounds, a class of compounds was studied in which N -> Si coordination served to stabilize a double bond between silicon and either sulfur phosphorus , nitrogen", oxygen or a transition metal " (e.g. 107). In these compounds the silicon is formally pentavalent, though it is coordinated to only four atoms. This topic belongs more appropriately to the chapter on silylenes, and is summarized here briefly for the sake of completeness. 

The number of covalent bonds formed by an atom is termed its COVALENCY. The covalency of an atom is equal to the number of electrons the atom needs to become isoelectronic with a noble gas. Some of the more common elements have the following covalencies when they follow the octet rule and also have no charge hydrogen and the halogens, 1 oxygen and sulfur, 2 nitrogen and phosphorus, 3 carbon and silicon, 4. LEWIS ELECTRONIC FORMULAS, in which bonds and unshared electrons are shown, are given for a few typical compounds of these elements ... 

HPLC is one of the most universal methods for determining the enantiomeric composition of substances and mixtures in a short time frame. Its application is not restricted to molecules in which chirality is based on a quaternary carbon atom with four different substituents it can also be employed for compounds containing a chiral silicon, nitrogen, sulfur, or phosphorus atom. Likewise, asymmetric sulfoxides or aziridines, the chirality of which is based on a lone electron pair, can be separated. Chirality can also be traced back to helical structures, as in the case of polymers and proteins to the existence of atropiso-merism, the hindered rotation about a single bond, as observed, for example, in the case of binaphthol, or to spiro compounds. 

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