Experimental and Theoretical EPR Study of Jahn−Teller-Active [HIPTN[subscript 3]N]MoL Complexes (L = N[subscript 2], CO, NH[subscript 3])
The trigonally symmetric Mo(III) coordination compounds [HIPTN[subscript 3]N]MoL (L = N[subscript 2], CO, NH[subscript 3]; [HIPTN3N]Mo = [(3,5-(2,4,6-i-Pr[subscript 3]C[subscript 6]H[subscript 2])[subscript 2]C[subscript 6]H[subscript 3]NCH[subscript 2]CH[subscript 2])[subscript 3]N]Mo) are low-spin...
| Main Authors: | , , , , , |
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| Other Authors: | |
| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2013
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| Online Access: | http://hdl.handle.net/1721.1/82552 https://orcid.org/0000-0001-5827-3552 |
| _version_ | 1826213657355223040 |
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| author | McNaughton, Rebecca L. Roemelt, Michael Chin, Jia Min Neese, Frank Hoffman, Brian M. Schrock, Richard Royce |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry McNaughton, Rebecca L. Roemelt, Michael Chin, Jia Min Neese, Frank Hoffman, Brian M. Schrock, Richard Royce |
| author_sort | McNaughton, Rebecca L. |
| collection | MIT |
| description | The trigonally symmetric Mo(III) coordination compounds [HIPTN[subscript 3]N]MoL (L = N[subscript 2], CO, NH[subscript 3]; [HIPTN3N]Mo = [(3,5-(2,4,6-i-Pr[subscript 3]C[subscript 6]H[subscript 2])[subscript 2]C[subscript 6]H[subscript 3]NCH[subscript 2]CH[subscript 2])[subscript 3]N]Mo) are low-spin d[superscript 3] (S = 1/2) species that exhibit a doubly degenerate [superscript 2]E ground state susceptible to a Jahn−Teller (JT) distortion. The EPR spectra of all three complexes and their temperature and solvent dependences are interpreted within a formal “two-orbital” model that reflects the ground-state configuration, describes the vibronic interactions that lead to the JT distortions, and addresses whether these complexes exhibit static or dynamic JT distortions. The electronic and vibronic properties of these complexes are then analyzed through ab initio quantum chemical computations. It is not possible to interpret the spectroscopic properties of the orbitally degenerate [HIPTN[subscript 3]N]MoL with DFT methods, so we have resorted to multi-reference wavefunction approaches, the entry level of which is the complete active space self-consistent field (CASSCF) method. Overall, the experimental and computational studies provide new insights into the role of trigonal coordination, as enforced by the [HIPTN[subscript 3]N][superscript 3−] ligand, in activating the Mo ion for the binding and reduction of N[subscript 2]. |
| first_indexed | 2024-09-23T15:52:45Z |
| format | Article |
| id | mit-1721.1/82552 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T15:52:45Z |
| publishDate | 2013 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/825522022-10-02T04:47:15Z Experimental and Theoretical EPR Study of Jahn−Teller-Active [HIPTN[subscript 3]N]MoL Complexes (L = N[subscript 2], CO, NH[subscript 3]) McNaughton, Rebecca L. Roemelt, Michael Chin, Jia Min Neese, Frank Hoffman, Brian M. Schrock, Richard Royce Massachusetts Institute of Technology. Department of Chemistry Chin, Jia Min Schrock, Richard Royce The trigonally symmetric Mo(III) coordination compounds [HIPTN[subscript 3]N]MoL (L = N[subscript 2], CO, NH[subscript 3]; [HIPTN3N]Mo = [(3,5-(2,4,6-i-Pr[subscript 3]C[subscript 6]H[subscript 2])[subscript 2]C[subscript 6]H[subscript 3]NCH[subscript 2]CH[subscript 2])[subscript 3]N]Mo) are low-spin d[superscript 3] (S = 1/2) species that exhibit a doubly degenerate [superscript 2]E ground state susceptible to a Jahn−Teller (JT) distortion. The EPR spectra of all three complexes and their temperature and solvent dependences are interpreted within a formal “two-orbital” model that reflects the ground-state configuration, describes the vibronic interactions that lead to the JT distortions, and addresses whether these complexes exhibit static or dynamic JT distortions. The electronic and vibronic properties of these complexes are then analyzed through ab initio quantum chemical computations. It is not possible to interpret the spectroscopic properties of the orbitally degenerate [HIPTN[subscript 3]N]MoL with DFT methods, so we have resorted to multi-reference wavefunction approaches, the entry level of which is the complete active space self-consistent field (CASSCF) method. Overall, the experimental and computational studies provide new insights into the role of trigonal coordination, as enforced by the [HIPTN[subscript 3]N][superscript 3−] ligand, in activating the Mo ion for the binding and reduction of N[subscript 2]. National Institutes of Health (U.S.) (GM31978) 2013-11-22T18:18:04Z 2013-11-22T18:18:04Z 2010-04 2010-01 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/82552 McNaughton, Rebecca L., Michael Roemelt, Jia Min Chin, Richard R. Schrock, Frank Neese, and Brian M. Hoffman. “Experimental and Theoretical EPR Study of Jahn−Teller-Active [HIPTN3N]MoL Complexes (L = N2, CO, NH3).” Journal of the American Chemical Society 132, no. 25 (June 30, 2010): 8645-8656. https://orcid.org/0000-0001-5827-3552 en_US http://dx.doi.org/10.1021/ja1004619 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) PMC |
| spellingShingle | McNaughton, Rebecca L. Roemelt, Michael Chin, Jia Min Neese, Frank Hoffman, Brian M. Schrock, Richard Royce Experimental and Theoretical EPR Study of Jahn−Teller-Active [HIPTN[subscript 3]N]MoL Complexes (L = N[subscript 2], CO, NH[subscript 3]) |
| title | Experimental and Theoretical EPR Study of Jahn−Teller-Active [HIPTN[subscript 3]N]MoL Complexes (L = N[subscript 2], CO, NH[subscript 3]) |
| title_full | Experimental and Theoretical EPR Study of Jahn−Teller-Active [HIPTN[subscript 3]N]MoL Complexes (L = N[subscript 2], CO, NH[subscript 3]) |
| title_fullStr | Experimental and Theoretical EPR Study of Jahn−Teller-Active [HIPTN[subscript 3]N]MoL Complexes (L = N[subscript 2], CO, NH[subscript 3]) |
| title_full_unstemmed | Experimental and Theoretical EPR Study of Jahn−Teller-Active [HIPTN[subscript 3]N]MoL Complexes (L = N[subscript 2], CO, NH[subscript 3]) |
| title_short | Experimental and Theoretical EPR Study of Jahn−Teller-Active [HIPTN[subscript 3]N]MoL Complexes (L = N[subscript 2], CO, NH[subscript 3]) |
| title_sort | experimental and theoretical epr study of jahn teller active hiptn subscript 3 n mol complexes l n subscript 2 co nh subscript 3 |
| url | http://hdl.handle.net/1721.1/82552 https://orcid.org/0000-0001-5827-3552 |
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