Low‐Valent Organometallics—Synthesis, Reactivity, and Potential Applications

Abstract

General concepts for the synthesis and stabilization of low-valent organometallic complexes of Groups 2, 12, 13, and 15 metals and common structural motifs are described. While kinetically stabilized complexes are in the focus for more than two decades, the principle of base-stabilization only recently allowed the synthesis of unforeseen compounds. As-prepared complexes not only show fascinating structural diversities, but exhibit also very interesting chemical properties. Low-valent complexes are of particular interest in the synthesis of novel molecular complexes, but may also find applications as tailor-made precursors for the synthesis of nanosized materials.

Synthesis, structure and bonding nature of heavy dipnictene radical anions

“…Heavy p-block element compounds with π-bonding contribution 1 have received increasing interest after the synthesis of the first stable diphosphene [Mes*P] 2 (Mes* = 2,4,6- t -Bu 3 -C 6 H 2 ) 2 and disilene [Mes 2 Si] 2 (Mes = 2,4,6-Me 3 -C 6 H 2 ) 3 in the 1980s. Heavier dipnictenes [RE] 2 (E = As, Sb, Bi) are typically kinetically stabilized by using bulky substituents, i.e.…”

Stable dimeric magnesium(i) compounds: from chemical landmarks to versatile reagents

“…1 Many of these advances are driven by the chemistry of low coordination and low oxidation state complexes displaying new bonding modes. 4,5 These compounds can often feature a set of frontier orbitals that allow novel stoichiometric or catalytic transformations, including the activation of typically unreactive small molecules that was traditionally solely associated with transition metal chemistry. 4 School of Chemistry, Monash University, Melbourne, PO Box 23,Victoria,3800, Australia.…”

Alkaline and alkaline earth metals

“…More general concepts for the synthesis and stabilisation of low-valent organometallic complexes of Groups 2, 12, 13, and 15 metals have also been discussed. 101,102 A review article has summarised efforts to develop efficient metal-based catalysts, including those based upon magnesium, for the immortal ring-opening polymerisation cyclic esters. 103 An overview of synthetic procedures for the synthesis of alkaline earth complexes has appeared, including a brief discussion on the shortcomings of specific methods.…”