Belli Dell’Amico, Daniela, Biagini, Paolo, Chiaberge, Stefano, Falchi, Lorenzo, Labella, Luca, Lezzerini, Marco, Marchetti, Fabio, and Samaritani, Simona
Partial hydrolysis (H 2 O/Ln molar ratio = ¼) of lanthanum di- iso -propylcarbamato complex, [La(O 2 CN i Pr 2 ) 3 ], 1 , afforded the tetranuclear μ-oxo derivative [La 4 O(O 2 CN i Pr 2 ) 10 ], 2 , which was structurally characterized by single crystal X-ray diffraction studies. The carbonato–carbamato derivative of lanthanum, [La 4 (CO 3 )(O 2 CNBu 2 ) 10 ], 3 , was prepared by extraction of lanthanum ions from aqueous solution into heptane by the NHBu 2 /CO 2 system. Partial hydrolysis (H 2 O/Ln molar ratio = ½) of N , N -di-iso-propylcarbamato complexes of neodymium, europium, gadolinium and terbium, [Ln(O 2 CN i Pr 2 ) 3 ], yielded the derivatives [Ln 2 (CO 3 )(O 2 CN i Pr 2 ) 4 ] (Ln = Nd, 4 , Eu, 5 , Gd, 6 ). Exhaustive hydrolysis of [Ln(O 2 CNR 2 ) 3 ] (Ln = Nd, Tb, R = Bu; Ln = Eu, Gd, R = i Pr, Bu) produced hydrated lanthanide carbonates, Ln 2 (CO 3 ) 3 · n H 2 O. For sake of comparison with a block d metal, the exhaustive hydrolysis of two copper(II) carbamato complexes, [Cu(O 2 CNEt 2 ) 2 (NHEt 2 )] 2 and [Cu(O 2 CN i Pr 2 ) 2 ], was carried out with formation in both cases of the hydrated basic carbonate Cu 2 (OH) 2 (CO 3 )· n H 2 O. The exhaustive hydrolysis of mixtures of cerium and lanthanum or cerium and terbium N , N -dibutylcarbamato complexes allowed the preparation of mixed oxides containing the two metals in the desired molar ratio, via the intermediate formation of the corresponding mixed carbonates. [ABSTRACT FROM AUTHOR]