Preparation and properties of the tungsten tris(imido) functional group

Persistent Link:
http://hdl.handle.net/10150/278281
Title:
Preparation and properties of the tungsten tris(imido) functional group
Author:
Rodgers, Paula Marie, 1967-
Issue Date:
1993
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 first tris(imido) complex of a group 6 transition metal, [Li(THF)₄][W(=NAr)₃Cl] (8) (Ar = 2,6 iPr-C₆H₃) was prepared from W(=NAr)₂Cl₂(THF)₂ (2) and 2 equiv of the corresponding lithium amide, LiNHAr in THF. Complex (8) crystallizes in the monoclinic space group P2(1/n) with a = 13.787 (4) Å, b = 17.348 (5) Å, c = 22.781 (8) Å, and β = 90.43 (3)° with Z = 4. The crystal contains discrete C₃ᵥ [W(=NAr)₃Cl]⁻ anions with imido W-N-C(ipso) angles averaging 170.8 (15)° and imido W-N bonds averaging 1.782 (15) Å. The neutral imido species W(=NAr)₃(PMe₃) (15) was made by adding 10 equiv of PMe₃ to (8). "Coupling" of the imido ligand in (15) with CO₂ and O=C=NR (R = Ph, ᵗBu) gave W[NArC(O)O] (=NAr)₂ PMe₃ (20) and W[NArC(O)NR](=NAr)₂PMe₃ (19) respectively. 2,6 Diisopropylaniline was added to (8) to give the complex W(=NAr)₂(NHAr)₂ (9). The chloride ligand of complex (8) was replaced by Li alkyl reagents to yield alkylated product [Li(THF)₄][W(=NAr)₃R] (R = Me, ᵗBu and Np') (11-13). The cation of (8) was substituted by adding ⁿBu₄NBr to afford [ⁿBu₄N][W(=NAr)₃Br] (10). These and related synthetic and reactivity studies will be described.
Type:
text; Thesis-Reproduction (electronic)
Keywords:
Chemistry, Inorganic.
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.titlePreparation and properties of the tungsten tris(imido) functional groupen_US
dc.creatorRodgers, Paula Marie, 1967-en_US
dc.contributor.authorRodgers, Paula Marie, 1967-en_US
dc.date.issued1993en_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 first tris(imido) complex of a group 6 transition metal, [Li(THF)₄][W(=NAr)₃Cl] (8) (Ar = 2,6 iPr-C₆H₃) was prepared from W(=NAr)₂Cl₂(THF)₂ (2) and 2 equiv of the corresponding lithium amide, LiNHAr in THF. Complex (8) crystallizes in the monoclinic space group P2(1/n) with a = 13.787 (4) Å, b = 17.348 (5) Å, c = 22.781 (8) Å, and β = 90.43 (3)° with Z = 4. The crystal contains discrete C₃ᵥ [W(=NAr)₃Cl]⁻ anions with imido W-N-C(ipso) angles averaging 170.8 (15)° and imido W-N bonds averaging 1.782 (15) Å. The neutral imido species W(=NAr)₃(PMe₃) (15) was made by adding 10 equiv of PMe₃ to (8). "Coupling" of the imido ligand in (15) with CO₂ and O=C=NR (R = Ph, ᵗBu) gave W[NArC(O)O] (=NAr)₂ PMe₃ (20) and W[NArC(O)NR](=NAr)₂PMe₃ (19) respectively. 2,6 Diisopropylaniline was added to (8) to give the complex W(=NAr)₂(NHAr)₂ (9). The chloride ligand of complex (8) was replaced by Li alkyl reagents to yield alkylated product [Li(THF)₄][W(=NAr)₃R] (R = Me, ᵗBu and Np') (11-13). The cation of (8) was substituted by adding ⁿBu₄NBr to afford [ⁿBu₄N][W(=NAr)₃Br] (10). These and related synthetic and reactivity studies will be described.en_US
dc.typetexten_US
dc.typeThesis-Reproduction (electronic)en_US
dc.subjectChemistry, Inorganic.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.proquest1352326en_US
dc.identifier.bibrecord.b27085569en_US
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