dc.contributor.advisor |
Masuda, Jason Douglas, 1977- |
|
dc.creator |
Giffin, Nicholas Allan |
|
dc.date.accessioned |
2013-07-03T13:11:07Z |
|
dc.date.available |
2013-07-03T13:11:07Z |
|
dc.date.issued |
2012 |
|
dc.identifier.other |
QD181 P1 G542 2012 |
|
dc.identifier.uri |
http://library2.smu.ca/xmlui/handle/01/25016 |
|
dc.description |
xviii, 164 leaves : ill. ; 29 cm. |
en_CA |
dc.description |
Includes abstract and appendices. |
|
dc.description |
Includes bibliographical references (leaves 155-164). |
|
dc.description.abstract |
The synthesis, characterization and preliminary reactivity of a new diphosphine is discussed. Calculations indicated a favorable dissociation of the central P-P bond, corresponding to roughly 100kJ/mol relaxation energy for the full system. Reactions of (Dipp[subscript 2]C[subscript 2] H[subscript 4]N[subscript 2]P)[subscript 2] with elemental phosphorus (P[subscript 4]), sulfur (S[subscript 8]), oxygen (O[subscript 2]), selenium (Se[superscript 0]) and tellurium (Te [superscript 0]) yielded the trans,trans-tetraphosphabicyclobutane (LP-P[subscript 4]-PL), persulfide/sulfide (LP-S-S-PL/LP-S-PL), ethereal oxidative products (LP(O)-O-(O)PL, LP(Se)-Se-PL) as well as bridging selenide (LP-Se-PL) and telluride (LP-Te-PL) species. Reactions with boranes (BR[subscript 3], R = H or C[subscript 6]F[subscript 5]) supported an FLP-type reactivity profile (LP[arrow right]BR3 ) and subsequent hydrogen abstraction forming LPH[arrow right]BR[subscript 3]. Activation of heteroallenes including CS[subscript 2], Ph-NCO, and Ph-NCS was achieved, forming the corresponding insertion products (LP-C(=R)-X-PL). The nucleophilic ring-opening of S[subscript 4]N[subscript 4] with carbenes was investigated. IMes formed IMes=N-S[subscript 3]N[subscript 3] while more electrophilic carbenes formed zwitterionic R-S-N-S[subscript 4]N[subscript 3] (R = SIPr, CAAC) structures. Introduction of nucleophilic solvents induced degradation of the S[subscript 3]N[subscript 3] rings to R=NSNSS (R = IMes, SIPr) structures. |
en_CA |
dc.description.provenance |
Submitted by Dianne MacPhee (dianne.macphee@smu.ca) on 2013-07-03T13:11:07Z
No. of bitstreams: 0 |
en |
dc.description.provenance |
Made available in DSpace on 2013-07-03T13:11:07Z (GMT). No. of bitstreams: 0
Previous issue date: 2012 |
en |
dc.language.iso |
en |
en_CA |
dc.publisher |
Halifax, N.S. : Saint Mary's University |
en_CA |
dc.subject.lcc |
QD181.P1 |
|
dc.subject.lcsh |
Phosphorus compounds |
|
dc.subject.lcsh |
Phosphine |
|
dc.subject.lcsh |
Radicals (Chemistry) |
|
dc.subject.lcsh |
Reactivity (Chemistry) |
|
dc.subject.lcsh |
Group 14 elements |
|
dc.subject.lcsh |
Group 15 elements |
|
dc.title |
Synthesis and reactivity of low-valent group 14-15 compounds |
en_CA |
dc.type |
Text |
en_CA |
thesis.degree.name |
Master of Science in Applied Science |
|
thesis.degree.level |
Masters |
|
thesis.degree.discipline |
Chemistry |
|
thesis.degree.grantor |
Saint Mary's University (Halifax, N.S.) |
|