This review is essentially an update of one entitled “πBonding and The Lone Pair Effect in Multiple Bonds Between Heavier Main Group Elements” which was published more than 10 years ago in this journal.1 The coverage of that survey was focused on the synthesis, structure, and bonding of stable compounds2 of heavier main group elements that correspond to the skeletal drawings reproduced in Tables 1 and 2. A row of numbers is listed at the bottom of each column in these tables. This refers to the number of stable complexes from each class that are currently known. The numbers in parentheses refer to the number of stable species that were known at the time of the previous review. Clearly, many of the compound classes listed have undergone considerable expansion although some remain stubbornly rare. The most significant developments for each class will be discussed in detail under the respective sections. As will be seen, there are also a limited number of multiple bonded heavier main group species that do not fit neatly in the classifications in Tables 1 and 2. However, to keep the review to a manageable length, the limits and exclusions, which parallel those used earlier, are summarized as follows: (i) discussion is mainly confined to compounds where experimental data on stable, isolated species have been obtained, (ii) stable compounds having multiple bonding between heavier main group elements and transition metals are not generally discussed, (iii) compounds in which a multiple bonded heavier main group element is incorporated within a ring are generally not covered, and (iv) hypervalent main group compounds that may incorporate faux multiple bonding are generally excluded. Such compounds are distinguished from those in Tables 1 and 2 in that they apparently require the use of more than four valence bonding orbitals at one or more of the bonded atoms. The remainder of this review is organized in a similar manner to that of the previous one wherein the compounds to be discussed are classified according to those summarized in Tables 1 and 2. The key unifying feature of almost all molecules discussed in this review is that they are generally stabilized by the use of bulky substituents which block associative or various decomposition pathways.3 Since the previous review was published in 1999, several review articles that cover parts of the subject matter have appeared.4

π-Bonding and the Lone Pair Effect in Multiple Bonds Involving Heavier Main Group Elements: Developments in the New Millennium

As valuable C1 building blocks, isocyanides represent an important class of reactive species and synthons. During the past decades, exhaustive efforts have been devoted to the discovery of highly efficient reactions involving isocyanide on the basis of the development of the Passerini and Ugi reactions. Several types of reactions involving isocyanides have been reported, such as nucleophilic attack, electrophilic addition, imidoylation reactions, and oxidation etc. In this review, recent progress in isocyanide insertion chemistry is presented. Among all isocyanide insertions, two catalytic systems have been developed, that is, Lewis (Bronsted) acid-catalyzed isocyanide insertions and transition-metal-enabled isocyanide insertions, respectively. This review is hence written in the sequence of Lewis (Bronsted) acid-catalyzed isocyanide insertion and transitional metal-enabled isocyanide insertion, where isocyanide insertion into heteroatom–hydrogen bonds, carbon–halogen bonds, carbon–hydrogen bonds, and metal carbenes are summarized.

Recent advances in isocyanide insertion chemistry

Isocyanides have long proved themselves to be irreplaceable building blocks in modern organic chemistry. The unique features of the isocyano group make isocyanides particularly useful for the synthesis of a number of important classes of nitrogen heterocycles, such as pyrroles, indoles, and quinolines. Several cocyclizations of isocyanides via zwitterions and radical intermediates as well as transition-metal-catalyzed syntheses of different types of heterocycles have recently been developed. Methods starting from isocyanides often have distinct advantages over alternative approaches to the same heterocycles because of their enhanced convergence, the great simplicity of most of the operations with them, and the great variety of isocyanides readily available for use. Isocyanides have also been used in some enantioselective syntheses of chiral heterocyclic compounds, including natural products as well as precursors thereof.

Isocyanides in the Synthesis of Nitrogen Heterocycles

Small inorganic rings in the 21st century: from fleeting intermediates to novel isolable entities.

Since the first heavy alkene analogues of germanium and tin were isolated in 1976, followed by West's disilene in 1981, the chemistry of stable group 14 dimetallenes and dimetallynes has advanced immensely. Recent developments in this field veered the focus from the isolation of novel bonding motifs to mimicking transition metals in their ability to activate small molecules and perform catalysis. The potential of these homonuclear multiply bonded compounds has been demonstrated numerous times in the activation of H2, NH3, CO2 and other small molecules. Hereby, the strong relationship between structure and reactivity warrants close attention towards rational ligand design. This minireview provides an overview on recent developments in regard to bond activation with group 14 dimetallenes and dimetallynes with the perspective of potential catalytic applications of these compounds.

/pdf/recent-advances-of-group-14-dimetallenes-and-dimetallynes-in-1i80n0ecau.pdf

Recent advances of group 14 dimetallenes and dimetallynes in bond activation and catalysis

Siliranes: Formation, isonitrile insertions, and thermal rearrangements

New compounds with Ge/Ge and Ge/C multiple bonds

Tris(triphenylplumbyl)plumbate: an anion with three stretched lead–lead bonds

Photolytisch aus Hexa-tert-butylcyclotrisilan erzeugtes Di-tert-butylsilylen reagiert mit Selenophen oder 2,5-Dimethyltellurophen unter Chalkogenabstraktion zum 1,3-Diselena-2,4-disiletan 6 und 1,3-Ditellura-2,4-disiletan 7. Die Rontgenstrukturanalysen von 6 und 7 zeigen das Vorliegen planarer Vierringe mit den kleineren endocyclischen Winkeln an den Chalkogen- und den groseren an den Siliciumatomen.



Silylene Reactions with Selenophene and a Tellurophene: Formation and Structures of a 1,3-Diselena-2,4-disiletane and a 1,3-Ditellura-2,4-disiletane [1]



Di-tert-butylsilylene, generated by photolysis of hexa-tert-butylcyclotrisilane, reacts with selenophene or 2,5-dimethyltellurophene by chalcogen abstraction to furnish the 1,3-diselena-2,4-disiletane 6 and 1,3-ditellura-2,4-disiletane 7 ring systems. The X-ray structure analyses of 6 and 7 reveal strictly planar four-membered rings with the smaller endocyclic angles at the chalcogen and the larger angles at the silicon atoms.

Silylen-Reaktionen mit Selenophen und einem Tellurophen: Bildung und Strukturen eines 1,3-Diselena-2,4-disiletans und eines 1,3-Ditellura-2,4-disiletans [1]

The siliranes 7–10 and 22 as well as the vinylsiliranes 14–16, 20 , and 21 are prepared by [1+2]-cycloadditions of silylene 2 with alkenes and dienes. The first isonitrile insertion products, the silacyclobutanimines 26–28 were synthesized and the structure of 28 was determined by X-ray crystallography. Upon thermolysis 20–22 rearranged quantitatively to furnish the compounds 29–32 .

Siliranes: Formation, Isonitrile Insertions, and Thermal Rearrangements.

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