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Donor and ate ‐Coordination in Rare‐Earth Metal Bis(dimethylsilyl)amide Complexes
Author(s) -
Meermann Christian,
Gerstberger Gisela,
Spiegler Michael,
Törnroos Karl W.,
Anwander Reiner
Publication year - 2008
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200800050
Subject(s) - chemistry , isostructural , trigonal bipyramidal molecular geometry , bifunctional , coordination complex , coordination geometry , crystallography , coordination sphere , molecule , adduct , denticity , nuclear magnetic resonance spectroscopy , amide , stereochemistry , square pyramidal molecular geometry , metal , crystal structure , hydrogen bond , catalysis , biochemistry , organic chemistry
Complete thf donor exchange is observed when complexes Ln[N(SiHMe 2 ) 2 ] 3 (thf) 2 (Ln = La, Nd) are treated with the monofunctional donor molecules triphenylphosphane oxide, N ‐methylimidazole, and 1,3‐dimethylimidazolin‐2‐ylidene. The resulting complexes Ln[N(SiHMe 2 ) 2 ] 3 (donor) 2 exhibit a trigonal‐bipyramidal coordination geometry with the donor molecules located in the apical positions. Bifunctional chelating donors 1,10‐phenanthroline, 1,2‐bis(dimethylphosphanyl)ethane, and N , N , N′ , N′ ‐tetramethylethylenediamine give discrete complexes Ln[N(SiHMe 2 ) 2 ] 3 (phen) (Ln = Sc, La, Nd), Nd[N(SiHMe 2 ) 2 ] 3 (dmpe), and La[N(SiHMe 2 ) 2 ] 3 (tmeda). The phen adducts are isostructural as demonstrated for the large Nd 3+ and small Sc 3+ centers by X‐ray structure analyses and display a distorted square‐pyramidal coordination geometry in the solid state. The distinct coordination of various donor molecules implies subtle changes of the Si–H bonding which can be straightforwardly examined by NMR and FTIR spectroscopy. Ate complex {Y[N(SiHMe 2 ) 2 ] 4 Li} 2 can be isolated and crystallized from Y(OTf) 3 –Li[N(SiHMe 2 ) 2 ]–hexane reaction mixtures. Dimerization is accomplished by unusual intermolecular Li ··· H–Si interactions.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)