Dichlorosilylene: a high temperature transient species to an indispensable building block

Isolating stable compounds with low-valent main group elements have long been an attractive research topic, because several of these compounds can mimic transition metals in activating small molecules. In addition, compounds with heavier low-valent main group elements have fundamentally different electronic properties when compared with their lighter congeners. Among group 14 elements, the heavier analogues of carbenes (R(2)C:) such as silylenes (R(2)Si:), germylenes (R(2)Ge:), stannylenes (R(2)Sn:), and plumbylenes (R(2)Pb:) are the most studied species with low-valent elements. The first stable carbene and silylene species were isolated as N-heterocycles. Among the dichlorides of group 14 elements, CCl(2) and SiCl(2) are highly reactive intermediates and play an important role in many chemical transformations. GeCl(2) can be stabilized as a dioxane adduct, whereas SnCl(2) and PbCl(2) are available as stable compounds. In the Siemens process, which produces electronic grade silicon by thermal decomposition of HSiCl(3) at 1150 °C, chemists proposed dichlorosilylene (SiCl(2)) as an intermediate, which further dissociates to Si and SiCl(4). Similarly, base induced disproportionation of HSiCl(3) or Si(2)Cl(6) to SiCl(2) is a known reaction. Trapping these products in situ with organic substrates suggested the mechanism for this reaction. In addition, West and co-workers reported a polymeric trans-chain like perchloropolysilane (SiCl(2))(n). However, the isolation of a stable free monomeric dichlorosilylene remained a challenge. The first successful attempt of taming SiCl(2) was the isolation of monochlorosilylene PhC(NtBu)(2)SiCl supported by an amidinate ligand in 2006. In 2009, we succeeded in isolating N-heterocyclic carbene (NHC) stabilized dichlorosilylene (NHC)SiCl(2) with a three coordinate silicon atom. (The NHC is 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) or 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes).) Notably, this method allows for the almost quantitative synthesis of (NHC)SiCl(2) without using any hazardous reducing agents. Dehydrochlorination of HSiCl(3) with NHC under mild reaction conditions produces (NHC)SiCl(2). We can separate the insoluble side product (NHC)HCl readily and recycle it to form NHC. The high yield and facile access to dichlorosilylene allow us to explore its chemistry to a greater extent. In this Account, we describe the results using (NHC)SiCl(2) primarily from our laboratory, including findings by other researchers. We emphasize the novel silicon compounds, which supposedly existed only as short-lived species. We also discuss silaoxirane, silaimine with tricoordinate silicon atom, silaisonitrile, and silaformyl chloride. In analogy with N-heterocyclic silylenes (NHSis), oxidative addition reactions of organic substrates with (NHC)SiCl(2) produce Si(IV) compounds. The presence of the chloro-substituents both on (NHC)SiCl(2) and its products allows metathesis reactions to produce novel silicon compounds with new functionality. These substituents also offer the possibility to synthesize interesting compounds with low-valent silicon by further reduction. Coordination of NHC to the silicon increases the acidity of the backbone protons on the imidazole ring, and therefore (NHC)SiCl(2) can functionalize NHC at the C-4 or C-5 position.