Carbene Stabilization of Highly Reactive Main-Group Molecules

Abstract

This article highlights recent efforts of this laboratory in the stabilization of highly reactive, low-oxidation-state, main-group molecules using bulky N-heterocyclic carbene ligands [L: = :C{N(2,6-Pr(i)(2)C(6)H(3))CH}(2); L': = :C{N(2,4,6-Me(3)C(6)H(2))CH}(2); L'': = :C{(i-Pr)NC(Me)}(2)]. The syntheses, structures, and computational studies of carbene-stabilized neutral diborenes [L:(H)B═B(H):L and L':(H)B═B(H):L'], a neutral Ga(6) octahedron (L'':Ga[Ga(4)Mes(4)]Ga:L''), disilicon (L:Si═Si:L), bis-silylene [L:(Cl)Si-Si(Cl):L], dipnictogens (L:E-E:L, E = P, As; L':P-P:L'), and parent phosphinidene (L:PH) are discussed. Some of the unique challenges associated with this "carbene-stabilization" strategy are also presented.

Functional Molecular Silicon Compounds I

“…With the powerful concept of stabilization of reactive main group species by strongly s-donating N-heterocyclic carbenes pioneered inter alia by Greg Robinson [7], some of Kipping's initial targets are now available as derivatives stabilized by coordination of N-heterocyclic carbenes. Eric Rivard (University of Alberta, Edmonton, Canada) summarizes this emerging new field from the point of view of low valent silicon chemistry in chapter titled "Recent Advances in the Heterocyclic Carbene-Supported Chemistry of Silicon" of Volume 2.…”

Synthesis and properties of heteroaromatic carbenes of the imidazole and triazole series and their fused analogues

“…During the discussion of such transformations, attention will be concentrated on structural rearrangements, and reactions with carbon and nitrogen electrophiles, particularly those with multiple bonds or nonmetals. The formation of complex compounds with metals and elementoelectrophiles of the main groups of the periodic table constitutes a very broad area, one that has been described in many reviews (see, for example, the most general of them [34][35][36][37] ). Therefore, except in those cases where elementoderivatives are used for the synthesis of new types of carbenes or reactions of their ring expansions, the results of these studies are not considered in the present work.…”

Synthesis of P2C2O2 and P2CO via NHC-mediated coupling of the phosphaethynolate anion

“…1 These fascinating molecules have provided insight into fundamental issues of structure and bonding and have spawned new applications in main group chemistry. Prominent examples germane to this report include main group diatomics and unusual heterocycles containing CO functionalities.…”