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Hafnium complexes stabilized by a macrocyclic ligand Corkin, James R.
Abstract
The goal of this thesis is to investigate the chemistry of hafnium complexes of the macrocyclic ligand, PhP(CH2SiMe2NSiMe2CH2)2PPh ([P2N2]). The hafnium dichloride, [P2N2]HfCl2 (1) is used as a starting material for all other compounds synthesized. 1 is isostructural with its zirconium analogue, [P2N2]ZrCl2 , but does not exhibit identical chemistry. While reaction of [P2N2]ZrCl2 with 2 equivalents of C8K under N2 resulted in formation of a zirconium dinitrogen compound, the same is not true for the hafnium analogue. Instead, the major product of the reaction of 1 with 2 equivalents of C8K is a hafnium dimer, {[P2N2]Hf}2 (2). [P2N2]HfI2 (3) is synthesized via the reaction of 1 with excess trimethylsilyliodide. Evidence will be presented that ([P2N2]Hf)2(μ-η2:η2-N2) (4) is the major product of the reaction between 3 and 2 equivalents of C8K under dinitrogen, while {[P2N2]Hf}2 (2) and [P2N2]Hf(C7H8) (5) appear to be minor products. Reaction of 1 with 2 equivalents of MeMgCl results in the formation of [P2N2]HfMe2 (6). The zirconium analogue of 6 reacts with toluene under an atmosphere of H2 to give [P2N2]Zr(C7H8), but this is not true for 6. Instead, reaction of 6 under H2 results in the formation of a hafnium tetrahydride, {[P2N2]Hf}2(μ-H)4 (7). A metathesis reaction of one equivalent of 1 with one equivalent of Mg(C4H6)(THF)2 results in formation of [P2N2]Hf(C4H6) (8). Unlike most mononuclear [P2N2] compounds, this compound exhibits 2 inequivalent phosphorus atoms evidenced by an AB doublet pattern in the 31P{1H} NMR spectrum. [Scientific formulae used in this abstract could not be reproduced.]
Item Metadata
Title |
Hafnium complexes stabilized by a macrocyclic ligand
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Creator | |
Publisher |
University of British Columbia
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Date Issued |
2000
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Description |
The goal of this thesis is to investigate the chemistry of hafnium complexes of the
macrocyclic ligand, PhP(CH2SiMe2NSiMe2CH2)2PPh ([P2N2]). The hafnium dichloride,
[P2N2]HfCl2 (1) is used as a starting material for all other compounds synthesized. 1 is
isostructural with its zirconium analogue, [P2N2]ZrCl2 , but does not exhibit identical
chemistry. While reaction of [P2N2]ZrCl2 with 2 equivalents of C8K under N2 resulted in
formation of a zirconium dinitrogen compound, the same is not true for the hafnium
analogue. Instead, the major product of the reaction of 1 with 2 equivalents of C8K is a
hafnium dimer, {[P2N2]Hf}2 (2).
[P2N2]HfI2 (3) is synthesized via the reaction of 1 with excess
trimethylsilyliodide. Evidence will be presented that ([P2N2]Hf)2(μ-η2:η2-N2) (4) is the
major product of the reaction between 3 and 2 equivalents of C8K under dinitrogen, while
{[P2N2]Hf}2 (2) and [P2N2]Hf(C7H8) (5) appear to be minor products.
Reaction of 1 with 2 equivalents of MeMgCl results in the formation of
[P2N2]HfMe2 (6). The zirconium analogue of 6 reacts with toluene under an atmosphere
of H2 to give [P2N2]Zr(C7H8), but this is not true for 6. Instead, reaction of 6 under H2
results in the formation of a hafnium tetrahydride, {[P2N2]Hf}2(μ-H)4 (7).
A metathesis reaction of one equivalent of 1 with one equivalent of
Mg(C4H6)(THF)2 results in formation of [P2N2]Hf(C4H6) (8). Unlike most mononuclear
[P2N2] compounds, this compound exhibits 2 inequivalent phosphorus atoms evidenced
by an AB doublet pattern in the 31P{1H} NMR spectrum. [Scientific formulae used in this abstract could not be reproduced.]
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Extent |
3296966 bytes
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Genre | |
Type | |
File Format |
application/pdf
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Language |
eng
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Date Available |
2009-07-07
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Provider |
Vancouver : University of British Columbia Library
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Rights |
For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use.
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DOI |
10.14288/1.0061360
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URI | |
Degree | |
Program | |
Affiliation | |
Degree Grantor |
University of British Columbia
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Graduation Date |
2000-05
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Campus | |
Scholarly Level |
Graduate
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Aggregated Source Repository |
DSpace
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Rights
For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use.