《Molecular modeling of the octacoordinated tetracarbonato-Nd(Ⅲ),[Nd(CO3)4]5-,complex and its nonacoordinated fluoro- and aquo-adducts》.pdfVIP

JOURNAL OF RARE EARTHS, Vol. 28, No. 6, Dec. 2010, p. 847 Molecular modeling of the octacoordinated tetracarbonato-Nd(III), 5– [Nd(CO ) ] , complex and its nonacoordinated fluoro- and aquo-adducts 3 4 1 2 2 S. P. Sinha , Alfredo M. Simas , Gustavo L. C. Moura (1. Scientific Research Development, 6565 Willowick Place, Dayton, Ohio 45459-3005, USA; 2. Departamento de Quimica Fundamental, CCEN, Universidade Federal de Pernambuco, 50590-470, Recife, PE, Brazil) Received 2 August 2010; revised 6 November 2010 Abstract: Theoretical investigation on the structures of the octacoordinated [Nd(CO ) ]5– and the nonacoordinated [Nd(CO ) .OH ]5– com- 3 4 3 4 2 plexes, using the SPARKLE parameters of the lanthanides within MOPAC, revealed that they possessed dodecahedral and square antipris- matic structures respectively with an average Nd–O distance of 0.249 nm. These structures and the Nd-O distances agreed well with those experimentally found in the crystal structures. Replacing the water molecule with a fluoride ion or a mondentatecarbonato ligand resulted in a nonacoordinated distorted square antiprismatic structures where the trans-carbonato groups were twisted. The corresponding decacoordinated structures with two fluoride ions or a bidentatecarbonato group, [Nd(CO3) ·F ]7– and [Nd(CO ) ]7–, were also investigated. In both cases con- 4 2 3 5 siderable twisting of the transcarbonato groups was observed. Keywords: lanthanides; theoretical; molecular models; octacoordination; carbonato co