| dc.contributor.author | Landry, Jeffrey C. | en_US |
| dc.date.accessioned | 2014-10-21T12:37:25Z | |
| dc.date.available | 2006 | |
| dc.date.issued | 2006 | en_US |
| dc.identifier.other | AAINR19604 | en_US |
| dc.identifier.uri | http://hdl.handle.net/10222/54843 | |
| dc.description | Reactions of primary amines (RNH2; R = 2,6-dimethylphenyl; Dmp, 2,6-diisopropylphenyl; Dipp) and pnictogen trihalides (PnX3, Pn = P; X = Cl, Br, Pn = As, Sb; X = Cl) were performed under various conditions. For Pn = phosphorus or arsenic, cyclodipnictazanes were formed in the presence of triethylamine. Subsequent addition of GaX3 to the cyclodipnictazanes effected a ring expansion reaction to new cationic 6-membered pnictazane rings. Similarly, addition of GaX3 to the cyclodipnictazanes, followed by in-situ addition of a strong Lewis base yields the neutral cyclotripnictazanes. Combinations of both cyclodipnictazanes (Pn = P, As) under ring expansion conditions produce cyclotripnictazanes with varying composition of both phosphorus and arsenic in the heterocycle as identified by mass spectrometry. The mechanism of the ring expansion has been explored leading to the isolation of a novel cationic 4-membered ring and a unique arsazene-arsine, which suggests cationic monomeric intermediates are involved in the reaction pathway. | en_US |
| dc.description | Corresponding reactions of RNH2 and SbCl3 do not yield the cyclodipnictazane but rather, in the presence of triethylamine produce the corresponding cyclotripnictazane. A dipnictadiazane (for Pn = Sb) has also been identified, which provides insight into the mechanism of dehydrohalide coupling reactions between primary amines and pnictogen trihalides.* | en_US |
| dc.description | *Please refer to dissertation for diagrams. | en_US |
| dc.description | Thesis (Ph.D.)--Dalhousie University (Canada), 2006. | en_US |
| dc.language | eng | en_US |
| dc.publisher | Dalhousie University | en_US |
| dc.publisher | | en_US |
| dc.subject | Chemistry, Organic. | en_US |
| dc.title | Pnictazane oligomers [RNPnX](n): Towards polypnictazanes . | en_US |
| dc.type | text | en_US |
| dc.contributor.degree | Ph.D. | en_US |
