Synthesis and characterization of multiple and metallacyclic imido compounds of the early transition metals

Persistent Link:
http://hdl.handle.net/10150/278101
Title:
Synthesis and characterization of multiple and metallacyclic imido compounds of the early transition metals
Author:
Allen, Kevin Dale, 1968-
Issue Date:
1992
Publisher:
The University of Arizona.
Rights:
Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
Abstract:
The bis(imido) complex Nb(=NAr)₂Cl(py)₂(Ar=2,6-diisopropylphenyl) reacts with two equivalents of LiNHAr in THF to form [Li(THF)₄)][Nb(=NAr)₂(NHAr)₂] (2). Likewise [Nb(NEt₂)₂Cl₃]₂ reacts with excess LiNHAr in THF to form 2. A similar neutral bis(imide) bis(amide) compound (9) of molybdenum has been made. Experiments are presented that suggest the (tris)imido functional group (Nb(=NAr)₃) - arises via an intermolecular deprotonation of [Nb(=NR)₂(NHR)₂]⁻. Complex 2 reacts with 1 equivalent of ᵗBuLi to form the tris(imide) amide [Li₂(THF)₄][Nb(=NAr)₃(NAr)] (6). Ta(OR)₂Cl₃(OEt₂) (OR=2,6-diisopropylphenoxide) reacts with excess 6-methylquinoline (6MQ) to form (η¹-(N)-6MQ)Ta(OR)₂Cl₃ (10). Compound 10 cannot be reduced to the η²-(N,C) product; however, (η₆-C₆Me₆)Ta(OR)₂Cl reacts with excess 6MQ to form (η²-(N,C)-6MQ)Ta(OR)₂Cl(Et₂O) (11), a precursor to metallacyclic imides and a proposed HDN intermediate. Compound 10 can be reduced to afford an unusual Ta(IV) complex (ηˣ-6MQ)Ta(OR)₂Cl₂ (12).
Type:
text; Thesis-Reproduction (electronic)
Keywords:
Chemistry, Inorganic.; Chemistry, Organic.
Degree Name:
M.S.
Degree Level:
masters
Degree Program:
Graduate College
Degree Grantor:
University of Arizona
Advisor:
Wigley, David E.

Full metadata record

DC FieldValue Language
dc.language.isoen_USen_US
dc.titleSynthesis and characterization of multiple and metallacyclic imido compounds of the early transition metalsen_US
dc.creatorAllen, Kevin Dale, 1968-en_US
dc.contributor.authorAllen, Kevin Dale, 1968-en_US
dc.date.issued1992en_US
dc.publisherThe University of Arizona.en_US
dc.rightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.en_US
dc.description.abstractThe bis(imido) complex Nb(=NAr)₂Cl(py)₂(Ar=2,6-diisopropylphenyl) reacts with two equivalents of LiNHAr in THF to form [Li(THF)₄)][Nb(=NAr)₂(NHAr)₂] (2). Likewise [Nb(NEt₂)₂Cl₃]₂ reacts with excess LiNHAr in THF to form 2. A similar neutral bis(imide) bis(amide) compound (9) of molybdenum has been made. Experiments are presented that suggest the (tris)imido functional group (Nb(=NAr)₃) - arises via an intermolecular deprotonation of [Nb(=NR)₂(NHR)₂]⁻. Complex 2 reacts with 1 equivalent of ᵗBuLi to form the tris(imide) amide [Li₂(THF)₄][Nb(=NAr)₃(NAr)] (6). Ta(OR)₂Cl₃(OEt₂) (OR=2,6-diisopropylphenoxide) reacts with excess 6-methylquinoline (6MQ) to form (η¹-(N)-6MQ)Ta(OR)₂Cl₃ (10). Compound 10 cannot be reduced to the η²-(N,C) product; however, (η₆-C₆Me₆)Ta(OR)₂Cl reacts with excess 6MQ to form (η²-(N,C)-6MQ)Ta(OR)₂Cl(Et₂O) (11), a precursor to metallacyclic imides and a proposed HDN intermediate. Compound 10 can be reduced to afford an unusual Ta(IV) complex (ηˣ-6MQ)Ta(OR)₂Cl₂ (12).en_US
dc.typetexten_US
dc.typeThesis-Reproduction (electronic)en_US
dc.subjectChemistry, Inorganic.en_US
dc.subjectChemistry, Organic.en_US
thesis.degree.nameM.S.en_US
thesis.degree.levelmastersen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.advisorWigley, David E.en_US
dc.identifier.proquest1348456en_US
dc.identifier.bibrecord.b27567254en_US
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