N,N-dialkylcarbamato metal complexes, molecular inorganic precursors to functionalized inorganic matrices

The relatively new class of the N,N-dialkylcarbamato metal complexes, of general formula [M(O2CNR2)n]m, n and m being the oxidation number of the central metal atom M and the nuclearity of the system, is reviewed with particular attention to compounds of Main Group elements (particularly tin, silicon and aluminium), and of transition d- and f-metals. Synthetic procedures and structural properties of the homoleptic compounds (i.e., compounds in which the set of anionic ligands is constituted by the monoanionic O2CNR2(−) ligand exclusively) are reported, also in relation to the results obtained by other research groups in this area. The reactivity of these systems is reported in connection with: (a) homoleptic derivatives; (b) non-homoleptic N,N-dialkylcarbamato complexes; (c) controlled hydrolysis of the homoleptic precursors to μ-oxo derivatives; (d) N,N-dialkylcarbamato complexes as reactive species towards surface hydroxyl groups, whereby Si–O–M linkages can be formed; (e) exhaustive hydrolysis of the N,N-dialkylcarbamato complexes; (f) metal N,N-dialkylcarbamato complexes as reactive intermediates to organic products. The literature references to papers originated from this research group can be found in the web site of the University of Pisa ().