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Synthesis, structure, and reactivity of diamidophosphine complexes of yttrium and the lanthanides

TitleSynthesis, structure, and reactivity of diamidophosphine complexes of yttrium and the lanthanides
Publication TypeJournal Article
Year of Publication2001
AuthorsFryzuk, MD, Yu, PH, Patrick, BO
JournalCanadian Journal of Chemistry-Revue Canadienne De Chimie
Volume79
Pagination1194-1200
Date PublishedJul
Type of ArticleArticle
ISBN Number0008-4042
Keywordsaluminum, BRIDGING N-2 UNIT, CATALYSTS, CRYSTAL-STRUCTURE, DINITROGEN, F-BLOCK METALS, lanthanides, LIGAND, lithium, mixed-donor ligands, NAPHTHALENE, OLEFIN POLYMERIZATION, SIDE-ON, TERTIARY PHOSPHINE COMPLEXES, YTTRIUM
Abstract

The reaction of the dilithiodiamidophosphine ligand precursor PhP(CH2SiMe2NPh)(2)Li-2(THF)(2)([NPN]Li-2(THF)(2)) with LnCl(3)(THF)(3) (Ln = Y, Sm, Ho. Yb. Lu; THF = tetrahydrofuran) in refluxing toluene generates the mononuclear complexes [NPN]LnCI(THF) in good yield. The molecular structures have been shown to be five-coordinate in the solid state and in solution. Attempts to prepare alkyl derivatives have only met with partial success; the reaction of MeMgCl with [NPN]YCl(THF) generates the partially characterized mixed-metal derivative [NPN]YMe2MgCl. The reaction with LiAlH4 results in complete ligand exchange and the formation of the tetranuclear lithium aluminum hydride derivative ([NPN]AlH2Li(THF))(2). Reduction of the lutetium derivative with KC8 and naphthalene generated the dinuclear naphthalene-bridged species {[NPN]Lu}(2)(mu-eta (4):eta (4)-C10H8) wherein each Lu centre engages in eta (4)-coordination to opposite sides of the arene moiety. X-ray crystallography was used to characterize the four complexes.

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