Silylated Group 14 Ylenes: An Emerging Class of Reactive Compounds

E-ISSN： 1099-0682|2015|23|3805-3820

ISSN： 1434-1948

Source： EUROPEAN JOURNAL OF INORGANIC CHEMISTRY (ELECTRONIC), Vol.2015, Iss.23, 2015-08, pp. : 3805-3820

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Abstract

AbstractSilyl‐substituted heavy‐element tetrylenes are very reactive entities and therefore prefer variously to dimerize to heavy olefin analogues, to oligomerize to cyclic products, or to undergo some type of rearrangement reaction. Our work on the synthesis of oligosilanyl‐substituted plumbylenes, stannylenes, and germylenes has shown that trapping such tetrylenes as phosphine adducts is a good method for preventing dimerization or rearrangement and allows the chemistry of the free tetrylene to be studied either through phosphane abstraction or even through thermally induced dissociation. In addition to a number of typical reactions with these tetrylenes, which occur in such a way that the divalent element becomes tetravalent, it was found in the case of germylenes that addition of monosubstituted alkynes proceeds by insertion into a Ge–Si bond with preservation of the divalent state of the germylene. The obtained tetrylene phosphane adducts could also be used as precursors for the generation of transition‐metal complexes with tetrylene ligands.