Cooperative strategies for CO homologation

Abstract

Recent approaches in which at least two metal or main-group centres are involved in the homologation of CO are reviewed.

Carbon Monoxide Coupling Reactions: A New Concept for the Formation of Hexahydroxybenzene

“…In the isolated deltate and squarate compounds, there are “substructural parts” (in red), which would support the concept of η 2 coordinated ethyne diolates as intermediates. In a very recent paper, Kong and Crimmin summarized cooperative strategies for CO homologation [18i] . Nevertheless, this possibility was not considered in all these papers [18]…”

Reductive Hexamerization of CO Involving Cooperativity Between Magnesium(I) Reductants and [Mo(CO)6]: Synthesis of Well‐Defined Magnesium Benzenehexolate Complexes**

“…In recent decades there has been a resurgence of interest in reactions involving the reductive homologation of CO, and the mechanisms by which they operate [4] . This is perhaps not surprising, considering the relationship of such reactions to the Fischer–Tropsch (F–T) process.…”

“…This utilizes CO gas as a C 1 building block, in combination with H 2 (that is, in syngas), to generate liquid hydrocarbons and oxygenates on a mega‐ton scale each year [5] . While the F–T process typically employs heterogeneous transition metal catalysts to operate, a considerable amount of attention is being paid to the use of organometallic compounds as soluble, homogeneous models for the study and optimization of F–T, and other C−C bond forming reactions that utilize CO as a feedstock [4, 6] …”

Main Group Multiple Bonds for Bond Activations and Catalysis

“…In addition to main group multiple bonds, low oxidation state and/or coordinate main group complexes have also undergone a renaissance in recent years. With several new breakthroughs revealing new classes of compounds, such as nucleophilic aluminyls, [21, 22] as well as advances in bond activations and catalysis [23–28] . The synthesis and bonding nature of main group multiple bonds have been reviewed recently [5, 6, 29–33] .…”