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Dinitrogen reduction by TmII, DyII, and NdII with simple amide and aryloxide ligands.
MedLine Citation:
PMID:  12515486     Owner:  NLM     Status:  PubMed-not-MEDLINE    
Abstract/OtherAbstract:
Dinitrogen can be reduced to the planar M2(mu-eta2:eta2-N2) structure without employing cyclopentadienyl or complicated polydentate ligands using the recently discovered divalent oxidation states of Tm(II), Dy(II), and Nd(II). Complexes of these ions with common monodentate amide and aryloxide ligands can effect N2 reduction. THF solutions of LnI2 (Ln = Tm, Dy) in the presence of 2 equiv of NaN(SiMe3)2 reduce dinitrogen to form {[(Me3Si)2N]2(THF)Ln}2(mu-eta2:eta2-N2) complexes that have planar Ln2N2 units and 1.264(7) and 1.305(6) A NN bonds consistent with (N2)2- moieties. With the stronger reductant Nd(II), aryloxides are sufficient ancillary ligands: the NdI2/2KOC6H3tBu2-2,6 (KOAr) system forms [(ArO)2(THF)2Nd]2(mu-eta2:eta2-N2), which has a 1.242(7) A NN bond.
Authors:
William J Evans; Gaël Zucchi; Joseph W Ziller
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Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  Journal of the American Chemical Society     Volume:  125     ISSN:  0002-7863     ISO Abbreviation:  J. Am. Chem. Soc.     Publication Date:  2003 Jan 
Date Detail:
Created Date:  2003-01-07     Completed Date:  2003-03-04     Revised Date:  2008-01-17    
Medline Journal Info:
Nlm Unique ID:  7503056     Medline TA:  J Am Chem Soc     Country:  United States    
Other Details:
Languages:  eng     Pagination:  10-1     Citation Subset:  -    
Affiliation:
Department of Chemistry, University of California, Irvine, CA 92697-2025, USA. wevans@uci.edu
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