Abstract
Following a related review dating back to 2003, the present review discusses in detail the various synthetic, structural and reactivity aspects of metal species containing one or more carbamato ligands, representing a large family of compounds across all the periodic table. A preliminary overview is provided on the reactivity of carbon dioxide with amines, and emphasis is given to recent findings concerning applications in various fields.
Highlights
The last two decades have witnessed an unprecedentedly intense effort of academic and industrial research in two main directions, i.e., to exploit CO2 as a C1 synthon for organic synthesis [5,6,7,8,9,10,11] and to develop more and more efficient systems able to capture and store CO2 [12,13]. The former goal is challenging for a variety of reactions, and a wide number of metal catalysts have been proposed to access valuable organic compounds and materials via CO2 fixation strategies, which, require harsh conditions in several cases [14,15]
It is worthy to note that, differently to other small molecules such as its relative carbon monoxide, carbon dioxide is a “bad” ligand for transition metals; examples of simple coordination compounds are relatively rare [16,17,18,19,20,21] and, metal catalysts working in CO2 activation routes usually exert their action without the intermediacy of metal-CO2 adducts
CO2 is prone to insertion reactions into a variety of metal-amide bonds, generating a carbamato ligand; metal complexes containing carbamato ligands are available through diverse synthetic routes not requiring the use of pressurized CO2
Summary
Deprotonation of a carbamic acid may be operated by a second basic group present in the structure of the employed amine (e.g., diamine), affording a zwitterionic carbamate. In the course of a study on the crystallization of amines assisted by 1,5-dichloro-trans-9,10diethynyl-9,10-dihydroanthracene-9,10-diol (DDDA), Mondal and Bhunia [75] found that cyclohexylamine (Scheme 3a), cycloheptylamine and piperidine undergo aerial carbonation affording the corresponding ammonium carbamate.
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