Mechanism and Scope of Phosphinidene Transfer from Dibenzo-7-phosphanorbornadiene Compounds
Dibenzo-7-phosphanorbornadiene compounds, RPA (A = C₁₄H₁₀ or anthracene), are investigated as phosphinidene sources upon thermally induced (70–90 °C) anthracene elimination. Analysis of substituent effects reveals that π-donating dialkylamide groups are paramount to successful phosphinidene transfer...
| Main Authors: | , , , , , |
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| Other Authors: | |
| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2018
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| Online Access: | http://hdl.handle.net/1721.1/117205 https://orcid.org/0000-0001-7445-5663 https://orcid.org/0000-0002-9239-7505 https://orcid.org/0000-0003-2568-3269 |
| _version_ | 1811080181462335488 |
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| author | García-Iriepa, Cristina Temprado, Manuel Transue, Wesley Velian, Alexandra Nava, Matthew Jordan Cummins, Christopher C |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry García-Iriepa, Cristina Temprado, Manuel Transue, Wesley Velian, Alexandra Nava, Matthew Jordan Cummins, Christopher C |
| author_sort | García-Iriepa, Cristina |
| collection | MIT |
| description | Dibenzo-7-phosphanorbornadiene compounds, RPA (A = C₁₄H₁₀ or anthracene), are investigated as phosphinidene sources upon thermally induced (70–90 °C) anthracene elimination. Analysis of substituent effects reveals that π-donating dialkylamide groups are paramount to successful phosphinidene transfer; poorer π-donors give reduced or no transfer. Substituent steric bulk is also implicated in successful transfer. Molecular beam mass spectrometry (MBMS) studies of each derivative reveal dialkylamide derivatives to be promising precursors for further gas-phase spectroscopic studies of phosphinidenes; in particular, we present evidence of direct detection of the dimethylamide derivative, [Me₂N═P]. Kinetic investigations of iPr₂NPA thermolysis in 1,3-cyclohexadiene and/or benzene-d₆ are consistent with a model of unimolecular fragmentation to yield free phosphinidene [iPr₂N═P] as a transient reactive intermediate. This conclusion is probed by density functional theory (DFT) calculations, which favored a mechanistic model featuring free singlet aminophosphinidenes. The breadth of phosphinidene acceptors is expanded to unsaturated substrates beyond 1,3-dienes to include olefins and alkynes; this provides a new synthetic route to valuable amino-substituted phosphiranes and phosphirenes, respectively. Stereoselective phosphinidene transfer to olefins is consistent with singlet phosphinidene reactivity by analogy with the Skell hypothesis for singlet carbene addition to olefins. |
| first_indexed | 2024-09-23T11:27:09Z |
| format | Article |
| id | mit-1721.1/117205 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T11:27:09Z |
| publishDate | 2018 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1172052022-09-27T19:39:08Z Mechanism and Scope of Phosphinidene Transfer from Dibenzo-7-phosphanorbornadiene Compounds Mechanism and Scope of Phosphinidene Transfer from Dibenzo-7-phosphanorbornadiene Compounds García-Iriepa, Cristina Temprado, Manuel Transue, Wesley Velian, Alexandra Nava, Matthew Jordan Cummins, Christopher C Massachusetts Institute of Technology. Department of Chemistry Cummins, Christopher C. Transue, Wesley Velian, Alexandra Nava, Matthew Jordan Cummins, Christopher C Dibenzo-7-phosphanorbornadiene compounds, RPA (A = C₁₄H₁₀ or anthracene), are investigated as phosphinidene sources upon thermally induced (70–90 °C) anthracene elimination. Analysis of substituent effects reveals that π-donating dialkylamide groups are paramount to successful phosphinidene transfer; poorer π-donors give reduced or no transfer. Substituent steric bulk is also implicated in successful transfer. Molecular beam mass spectrometry (MBMS) studies of each derivative reveal dialkylamide derivatives to be promising precursors for further gas-phase spectroscopic studies of phosphinidenes; in particular, we present evidence of direct detection of the dimethylamide derivative, [Me₂N═P]. Kinetic investigations of iPr₂NPA thermolysis in 1,3-cyclohexadiene and/or benzene-d₆ are consistent with a model of unimolecular fragmentation to yield free phosphinidene [iPr₂N═P] as a transient reactive intermediate. This conclusion is probed by density functional theory (DFT) calculations, which favored a mechanistic model featuring free singlet aminophosphinidenes. The breadth of phosphinidene acceptors is expanded to unsaturated substrates beyond 1,3-dienes to include olefins and alkynes; this provides a new synthetic route to valuable amino-substituted phosphiranes and phosphirenes, respectively. Stereoselective phosphinidene transfer to olefins is consistent with singlet phosphinidene reactivity by analogy with the Skell hypothesis for singlet carbene addition to olefins. 2018-07-30T18:51:55Z 2018-07-30T18:51:55Z 2017-08 2017-05 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/117205 Transue, Wesley J. et al. “Mechanism and Scope of Phosphinidene Transfer from Dibenzo-7-Phosphanorbornadiene Compounds.” Journal of the American Chemical Society 139, 31 (July 2017): 10822–10831 © 2017 American Chemical Society https://orcid.org/0000-0001-7445-5663 https://orcid.org/0000-0002-9239-7505 https://orcid.org/0000-0003-2568-3269 en_US http://dx.doi.org/10.1021/jacs.7b05464 Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) Prof. Cummins via Erja Kajosalo |
| spellingShingle | García-Iriepa, Cristina Temprado, Manuel Transue, Wesley Velian, Alexandra Nava, Matthew Jordan Cummins, Christopher C Mechanism and Scope of Phosphinidene Transfer from Dibenzo-7-phosphanorbornadiene Compounds |
| title | Mechanism and Scope of Phosphinidene Transfer from Dibenzo-7-phosphanorbornadiene Compounds |
| title_full | Mechanism and Scope of Phosphinidene Transfer from Dibenzo-7-phosphanorbornadiene Compounds |
| title_fullStr | Mechanism and Scope of Phosphinidene Transfer from Dibenzo-7-phosphanorbornadiene Compounds |
| title_full_unstemmed | Mechanism and Scope of Phosphinidene Transfer from Dibenzo-7-phosphanorbornadiene Compounds |
| title_short | Mechanism and Scope of Phosphinidene Transfer from Dibenzo-7-phosphanorbornadiene Compounds |
| title_sort | mechanism and scope of phosphinidene transfer from dibenzo 7 phosphanorbornadiene compounds |
| url | http://hdl.handle.net/1721.1/117205 https://orcid.org/0000-0001-7445-5663 https://orcid.org/0000-0002-9239-7505 https://orcid.org/0000-0003-2568-3269 |
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