Syntheses and studies of group 6 terminal pnictides, early-metal trimetaphosphate complexes, and a new bis-enamide ligand
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2011.
| Main Author: | |
|---|---|
| Other Authors: | |
| Format: | Thesis |
| Language: | eng |
| Published: |
Massachusetts Institute of Technology
2011
|
| Subjects: | |
| Online Access: | http://hdl.handle.net/1721.1/65264 |
| _version_ | 1811083314571771904 |
|---|---|
| author | Clough, Christopher Robert |
| author2 | Christopher C. Cummins. |
| author_facet | Christopher C. Cummins. Clough, Christopher Robert |
| author_sort | Clough, Christopher Robert |
| collection | MIT |
| description | Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2011. |
| first_indexed | 2024-09-23T12:30:48Z |
| format | Thesis |
| id | mit-1721.1/65264 |
| institution | Massachusetts Institute of Technology |
| language | eng |
| last_indexed | 2024-09-23T12:30:48Z |
| publishDate | 2011 |
| publisher | Massachusetts Institute of Technology |
| record_format | dspace |
| spelling | mit-1721.1/652642019-04-11T03:21:45Z Syntheses and studies of group 6 terminal pnictides, early-metal trimetaphosphate complexes, and a new bis-enamide ligand Clough, Christopher Robert Christopher C. Cummins. Massachusetts Institute of Technology. Dept. of Chemistry. Massachusetts Institute of Technology. Dept. of Chemistry. Chemistry. Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2011. Vita. Cataloged from PDF version of thesis. Includes bibliographical references. Investigated herein is the reactivity of the terminal-nitrido, trisanilide tungsten complex, NW(N[i- Pr]Ar)3 (Ar = 3,5-Me 2C6H3, 1). Nitride 1 has been shown to undergo an "N for (O)C1 metathesis with a variety of acid chlorides to form oxochloride (Ar[i-Pr]N) 3W(O)C1 (2) and the corresponding nitriles. The reaction of 1 with acid chlorides has been shown to proceed through an acylimido chloride intermediate. Furthermore, oxochloride 2 has been converted to a terminal phosphido trisanilide tungsten complex, PW(N[i-Pr]Ar)3 (9) by treatment with the anionic niobium phosphide complex [Na(OEt2)][PNb(N[Np]Ar) 31. Nitride 1 and oxochloride 2 have been converted to pseudo-octahedral complexes through the use of electrophilic reagents such as oxalyl chloride and phosphorus pentachloride. (Ar[i- Pr]N)3W(OCN)(Cl) 2 (10) and (Ar[i-Pr]N)3W(N=PCl3)(Cl) 2 (11) are synthesized by treating compound 1 with oxalyl chloride and PCl5, respectively. Similarly, (Ar[i-Pr]N) 3W(Cl) 3 (12) is formed by treatment of oxochloride 2 with PC15 with concomitant loss of oxyphosphorus trichloride. Reaction studies of trichloride 12 undertaken in the attempt to generate a low-coordinate tungsten species are also presented. Also reported presently is a new procedure for synthesis of the terminal phosphoryl complex (Ar[t-Bu]N)3MoPO (17) by treating phosphide (Ar[t-Bu]N) 3MoP (16) with the potent oxygen atom transfer (OAT) reagent mesitylnitrile oxide (MesCNO). In conjunction with collaborators, the thermodynamic and kinetic aspects of MesCNO as an OAT reagent with phosphide 16 and phosphines have been investigated. Density Functional Theory calculations of OAT reactions of MesCNO are also shown. In an effort to further develop the coordination chemistry of the trianionic, tridentate ligand trimetaphosphate, studies are described whereupon trimetaphosphate is metallated with molybdenum. (MeCN)3Mo(CO) 3 reacts with [PPN] 3[P30 9] -H20 ([PPN] = [Ph3P=N-PPh3]') to form the trimetaphosphate salt [PPN]3[(P30 9)Mo(CO) 3] ([PPN] 3[18]) in high yield. Efforts to generate trimetaphosphate vanadium oxo ((P30 9)V--O, 19) are also revealed. Finally, the synthesis of a new bis-enamide ligand class is described by the double addition of ketenimines to dilithium arylphosphanides. Formation of [Li(thf)]2 {PhP[C(CPh2)NPh] 21 ([Li(thf)] 2[20]) and [Li(thf)]2{MesP[C(CPh2)NPh] 2} ([Li(thf)]2[21]) are presented. The synthesis of tantalum species utilizing these new bis-enamide ligands is also demonstrated. by Christopher Robert Clough. Ph.D. 2011-08-18T19:10:36Z 2011-08-18T19:10:36Z 2011 2011 Thesis http://hdl.handle.net/1721.1/65264 743311794 eng M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission. http://dspace.mit.edu/handle/1721.1/7582 155 p. application/pdf Massachusetts Institute of Technology |
| spellingShingle | Chemistry. Clough, Christopher Robert Syntheses and studies of group 6 terminal pnictides, early-metal trimetaphosphate complexes, and a new bis-enamide ligand |
| title | Syntheses and studies of group 6 terminal pnictides, early-metal trimetaphosphate complexes, and a new bis-enamide ligand |
| title_full | Syntheses and studies of group 6 terminal pnictides, early-metal trimetaphosphate complexes, and a new bis-enamide ligand |
| title_fullStr | Syntheses and studies of group 6 terminal pnictides, early-metal trimetaphosphate complexes, and a new bis-enamide ligand |
| title_full_unstemmed | Syntheses and studies of group 6 terminal pnictides, early-metal trimetaphosphate complexes, and a new bis-enamide ligand |
| title_short | Syntheses and studies of group 6 terminal pnictides, early-metal trimetaphosphate complexes, and a new bis-enamide ligand |
| title_sort | syntheses and studies of group 6 terminal pnictides early metal trimetaphosphate complexes and a new bis enamide ligand |
| topic | Chemistry. |
| url | http://hdl.handle.net/1721.1/65264 |
| work_keys_str_mv | AT cloughchristopherrobert synthesesandstudiesofgroup6terminalpnictidesearlymetaltrimetaphosphatecomplexesandanewbisenamideligand |