Uranium Metalla-Allenes with Carbene Imido R2C=UIV=NR′ Units (R=Ph2PNSiMe3; R′=CPh3): Alkali-Metal-Mediated push–pull effects with an Amido Auxiliary
We report uranium(IV)-carbene-imido-amide metalla-allene complexes [U(BIPMTMS)(NCPh3)(NHCPh3)(M)] (BIPMTMS=C(PPh2NSiMe3)2; M=Li or K) that can be described as R2C=U=NR′ push–pull metalla-allene units, as organometallic counterparts of the well-known push–pull organic allenes. The solid-state structu...
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| Format: | Article |
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Wiley
2016
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| Online Access: | https://eprints.nottingham.ac.uk/46649/ |
| _version_ | 1848797377244168192 |
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| author | Lu, Erli Tuna, Floriana Lewis, William Kaltsoyannis, Nikolas Liddle, Stephen T. |
| author_facet | Lu, Erli Tuna, Floriana Lewis, William Kaltsoyannis, Nikolas Liddle, Stephen T. |
| author_sort | Lu, Erli |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | We report uranium(IV)-carbene-imido-amide metalla-allene complexes [U(BIPMTMS)(NCPh3)(NHCPh3)(M)] (BIPMTMS=C(PPh2NSiMe3)2; M=Li or K) that can be described as R2C=U=NR′ push–pull metalla-allene units, as organometallic counterparts of the well-known push–pull organic allenes. The solid-state structures reveal that the R2C=U=NR′ units adopt highly unusual cis-arrangements, which are also reproduced by gas-phase theoretical studies conducted without the alkali metals to remove their potential structure-directing roles. Computational studies confirm the double-bond nature of the U=NR′ and U=CR2 interactions, the latter increasingly attenuated by potassium then lithium when compared to the hypothetical alkali-metal-free anion. Combined experimental and theoretical data show that the push–pull effect induced by the alkali metal cations and amide auxiliary gives a fundamental and tunable structural influence over the C=UIV=N units. |
| first_indexed | 2025-11-14T20:02:54Z |
| format | Article |
| id | nottingham-46649 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T20:02:54Z |
| publishDate | 2016 |
| publisher | Wiley |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-466492020-05-04T17:58:34Z https://eprints.nottingham.ac.uk/46649/ Uranium Metalla-Allenes with Carbene Imido R2C=UIV=NR′ Units (R=Ph2PNSiMe3; R′=CPh3): Alkali-Metal-Mediated push–pull effects with an Amido Auxiliary Lu, Erli Tuna, Floriana Lewis, William Kaltsoyannis, Nikolas Liddle, Stephen T. We report uranium(IV)-carbene-imido-amide metalla-allene complexes [U(BIPMTMS)(NCPh3)(NHCPh3)(M)] (BIPMTMS=C(PPh2NSiMe3)2; M=Li or K) that can be described as R2C=U=NR′ push–pull metalla-allene units, as organometallic counterparts of the well-known push–pull organic allenes. The solid-state structures reveal that the R2C=U=NR′ units adopt highly unusual cis-arrangements, which are also reproduced by gas-phase theoretical studies conducted without the alkali metals to remove their potential structure-directing roles. Computational studies confirm the double-bond nature of the U=NR′ and U=CR2 interactions, the latter increasingly attenuated by potassium then lithium when compared to the hypothetical alkali-metal-free anion. Combined experimental and theoretical data show that the push–pull effect induced by the alkali metal cations and amide auxiliary gives a fundamental and tunable structural influence over the C=UIV=N units. Wiley 2016-08-01 Article PeerReviewed Lu, Erli, Tuna, Floriana, Lewis, William, Kaltsoyannis, Nikolas and Liddle, Stephen T. (2016) Uranium Metalla-Allenes with Carbene Imido R2C=UIV=NR′ Units (R=Ph2PNSiMe3; R′=CPh3): Alkali-Metal-Mediated push–pull effects with an Amido Auxiliary. Chemistry - A European Journal, 22 (33). pp. 11554-11558. ISSN 1521-3765 http://onlinelibrary.wiley.com/doi/10.1002/chem.201602603/abstract doi:10.1002/chem.201602603 doi:10.1002/chem.201602603 |
| spellingShingle | Lu, Erli Tuna, Floriana Lewis, William Kaltsoyannis, Nikolas Liddle, Stephen T. Uranium Metalla-Allenes with Carbene Imido R2C=UIV=NR′ Units (R=Ph2PNSiMe3; R′=CPh3): Alkali-Metal-Mediated push–pull effects with an Amido Auxiliary |
| title | Uranium Metalla-Allenes with Carbene Imido R2C=UIV=NR′ Units (R=Ph2PNSiMe3; R′=CPh3): Alkali-Metal-Mediated push–pull effects with an Amido Auxiliary |
| title_full | Uranium Metalla-Allenes with Carbene Imido R2C=UIV=NR′ Units (R=Ph2PNSiMe3; R′=CPh3): Alkali-Metal-Mediated push–pull effects with an Amido Auxiliary |
| title_fullStr | Uranium Metalla-Allenes with Carbene Imido R2C=UIV=NR′ Units (R=Ph2PNSiMe3; R′=CPh3): Alkali-Metal-Mediated push–pull effects with an Amido Auxiliary |
| title_full_unstemmed | Uranium Metalla-Allenes with Carbene Imido R2C=UIV=NR′ Units (R=Ph2PNSiMe3; R′=CPh3): Alkali-Metal-Mediated push–pull effects with an Amido Auxiliary |
| title_short | Uranium Metalla-Allenes with Carbene Imido R2C=UIV=NR′ Units (R=Ph2PNSiMe3; R′=CPh3): Alkali-Metal-Mediated push–pull effects with an Amido Auxiliary |
| title_sort | uranium metalla-allenes with carbene imido r2c=uiv=nr′ units (r=ph2pnsime3; r′=cph3): alkali-metal-mediated push–pull effects with an amido auxiliary |
| url | https://eprints.nottingham.ac.uk/46649/ https://eprints.nottingham.ac.uk/46649/ https://eprints.nottingham.ac.uk/46649/ |