π-Bonding and the Lone Pair Effect in Multiple Bonds between Heavier Main Group Elements

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

Amine- and phosphine-borane adducts: new interest in old molecules.

Mechanism of the Ligand-Free CuI-Catalyzed Azide–Alkyne Cycloaddition Reaction†

Chemists today are increasingly fascinated by gold’s unique position in the family of elements. In this review, the author looks at important new results emerging from recent research in gold chemistry.

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The fascinating implications of new results in gold chemistry

The pale yellow, solid silaketimine But2N–SiBut3 has been prepared and structurally characterized [SiN 1.568(3)A, Si–N–Si 177.8(2)°]; it forms a stable adduct with tetrahydrofuran by complexation of the unsaturated silicon atom.

Preparation and structure of a stable molecule containing a silicon nitrogen double bond and of its tetrahydrofuran adduct

Coordination‐Polymeric Paracyclophane Complexes of Copper and Silver

Unsaturated silicon compounds. 19. Compounds of silicon. 71. Donor adducts of the stable silaethene Me2Si:C(SiMe3) (SiMe-t-Bu2): properties and structures

Gabriele Reber

Papers

Preparation and structure of a stable molecule containing a silicon nitrogen double bond and of its tetrahydrofuran adduct

Coordination‐Polymeric Paracyclophane Complexes of Copper and Silver

Unsaturated silicon compounds. 19. Compounds of silicon. 71. Donor adducts of the stable silaethene Me2Si:C(SiMe3) (SiMe-t-Bu2): properties and structures

Structural correlations between trans- and cis-bis(diphenylphosphino)ethene, bis(diphenylphosphino)methane and their chlorogold(I) complexes

Isovalent and Mixed‐Valent Ylide Complexes of Gold: The Synthesis of Trinuclear Compounds Having Double Paddlewheel Structure