N,N-Dialkylcarbamato complexes as precursors for the chemical implantation of metal cations on a silica support

Recent Advances in the Chemistry of Metal Carbamates

“…In addition, the grafted carbamato complex may undergo subsequent chemical modifications. For instance, noble metals such as Cu, Pd and Pt can be chemically or thermally reduced to give the respective silica-supported metal nanoparticles [361,362,365]. Another post-functionalization strategy entails the introduction of additional ligands by replacement of the residual carbamates, and for instance this method has been adopted to introduce chiral β-diketonates on lanthanide-grafted carbamates for chiroptical luminescence applications [153,363].…”

“…The ensuing “grafting reaction” consists in the protonation of the carbamato moiety, with consequent release of CO 2 and the amine, and binding of the metal atom to the silica as a siloxide unit ( Scheme 44 b). Despite a possible molar excess of surface silanols (vide infra), a limited number of carbamato ligands per metal complex are involved in the process, and solid-state spectroscopic measurements (IR, NMR, EPR) agree in that the final metal fragment retains its nuclearity and the geometry of the residual ligands [ 131 , 234 , 360 , 361 ]. In other words, the grafting reaction allows the chemical implantation of tailored metal fragments over the surface of silica.…”

Synthesis and Structural Characterization of Non‐Homoleptic Carbamato Complexes of VV and WVI and Their Facile Implantation onto Silica Surfaces

“…It has been shown that cationic implantation onto silica can be effectively carried out with group‐four metals, niobium and tantalum, tin(IV), palladium(II), platinum(II), gold(I), copper(II) and lanthanides, by using N , N ‐dialkylcarbamato complexes of the general formula M(O 2 CNR 2 ) n as precursors.…”

Nanocrystalline Lanthanide Nitride Materials Synthesised by Thermal Treatment of Amido and Ammine Metallocenes: X‐ray Studies and DFT Calculations

“…Although oxidic rare-earth materials are still dominant, [1][2][3][4][5][6][7] nitridic rare-earth compounds are gaining more and more importance as they often exhibit even better material properties. Advances in the fields of semi-and superconductivity, [8][9][10] heterogeneous and homogeneous catalysis, [11][12][13] and the development of novel phosphor materials for highly efficient white-light-emitting phosphor-converted diodes [14,15] are prominent examples that prove that nitride chemistry of the rare-earth elements is full of exciting reactions and useful applications.…”