A Rhodium-Pentane Sigma-Alkane Complex: Characterization in the Solid State by Experimental and Computational Techniques
The pentane σ‐complex [Rh{Cy2P(CH2CH2)PCy2}(η2:η2‐C5H12)][BArF4] is synthesized by a solid/gas single‐crystal to single‐crystal transformation by addition of H2 to a precursor 1,3‐pentadiene complex. Characterization by low temperature single‐crystal X‐ray diffraction (150 K) and SSNMR spectroscopy...
Gespeichert in:
| Veröffentlicht in: | Angewandte Chemie International Edition 2016-03, Vol.55 (11), p.3677-3681 |
|---|---|
| Hauptverfasser: | , , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 3681 |
|---|---|
| container_issue | 11 |
| container_start_page | 3677 |
| container_title | Angewandte Chemie International Edition |
| container_volume | 55 |
| creator | Chadwick, F. Mark Rees, Nicholas H. Weller, Andrew S. Krämer, Tobias Iannuzzi, Marcella Macgregor, Stuart A. |
| description | The pentane σ‐complex [Rh{Cy2P(CH2CH2)PCy2}(η2:η2‐C5H12)][BArF4] is synthesized by a solid/gas single‐crystal to single‐crystal transformation by addition of H2 to a precursor 1,3‐pentadiene complex. Characterization by low temperature single‐crystal X‐ray diffraction (150 K) and SSNMR spectroscopy (158 K) reveals coordination through two Rh⋅⋅⋅H−C interactions in the 2,4‐positions of the linear alkane. Periodic DFT calculations and molecular dynamics on the structure in the solid state provide insight into the experimentally observed Rh⋅⋅⋅H−C interaction, the extended environment in the crystal lattice and a temperature‐dependent pentane rearrangement implicated by the SSNMR data.
Pentane takes a walk: The pentane sigma complex [Rh{Cy2P(CH2CH2)PCy2}(η2:η2‐C5H12)][BArF4] can be synthesized by a solid/gas single‐crystal to single‐crystal transformation. Periodic DFT calculations, molecular dynamics, and NMR spectroscopy provided insights into the fluxional processes occurring in the solid state. |
| doi_str_mv | 10.1002/anie.201511269 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_pubme</sourceid><recordid>TN_cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_4797708</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>3966533681</sourcerecordid><originalsourceid>FETCH-LOGICAL-c7079-6f75cb1a3b4dc9f475e8f8f8104b039096dff80c708c232bb5e7a29191be40b73</originalsourceid><addsrcrecordid>eNqFkc9v0zAUxy0EYr-4ckSRuOyS4hcndswBqVRdmZjKRId2tOzEWbw5cYkTaPfX46yjGhxAPvjZ_ny_-j4_hF4DngDGyTvZGj1JMGQACeXP0CFkCcSEMfI81CkhMcszOEBH3t8GPs8xfYkOEhoKQvAh2kyjr7UrzdDEl7rtZaujlblpZDy1d-Nh5pq11Zv30ayWnSx63Zl72RvXRqaN-jrQzpoyWvWy15HaRvPNOiDNaGUj2ZYPBkP_IAk3V7qoW_N90P4Evaik9frV436Mvp3Nr2af4osvi_PZ9CIuGGY8phXLCgWSqLQseJWyTOdVWIBThQnHnJZVleMA50VCEqUyzWTCgYPSKVaMHKMPO9_1oBpdFiFZJ61Yh5Cy2wonjfjzpTW1uHE_RMo4C67B4PTRoHNj8F40xhfa2vA9bvACGOU8JwxDQN_-hd66oQt9B4pjSimw5N8UozkFIGTMPdlRRee873S1jwxYjKMX4-jFfvRB8OZpo3v896wDwHfAT2P19j92Yro8nz81j3da43u92WtldycoIywT18uF-Li6XiwX2WexIr8A2kLK4g</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1768611337</pqid></control><display><type>article</type><title>A Rhodium-Pentane Sigma-Alkane Complex: Characterization in the Solid State by Experimental and Computational Techniques</title><source>Wiley Online Library - AutoHoldings Journals</source><creator>Chadwick, F. Mark ; Rees, Nicholas H. ; Weller, Andrew S. ; Krämer, Tobias ; Iannuzzi, Marcella ; Macgregor, Stuart A.</creator><creatorcontrib>Chadwick, F. Mark ; Rees, Nicholas H. ; Weller, Andrew S. ; Krämer, Tobias ; Iannuzzi, Marcella ; Macgregor, Stuart A.</creatorcontrib><description>The pentane σ‐complex [Rh{Cy2P(CH2CH2)PCy2}(η2:η2‐C5H12)][BArF4] is synthesized by a solid/gas single‐crystal to single‐crystal transformation by addition of H2 to a precursor 1,3‐pentadiene complex. Characterization by low temperature single‐crystal X‐ray diffraction (150 K) and SSNMR spectroscopy (158 K) reveals coordination through two Rh⋅⋅⋅H−C interactions in the 2,4‐positions of the linear alkane. Periodic DFT calculations and molecular dynamics on the structure in the solid state provide insight into the experimentally observed Rh⋅⋅⋅H−C interaction, the extended environment in the crystal lattice and a temperature‐dependent pentane rearrangement implicated by the SSNMR data.
Pentane takes a walk: The pentane sigma complex [Rh{Cy2P(CH2CH2)PCy2}(η2:η2‐C5H12)][BArF4] can be synthesized by a solid/gas single‐crystal to single‐crystal transformation. Periodic DFT calculations, molecular dynamics, and NMR spectroscopy provided insights into the fluxional processes occurring in the solid state.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201511269</identifier><identifier>PMID: 26880330</identifier><identifier>CODEN: ACIEAY</identifier><language>eng</language><publisher>Germany: Blackwell Publishing Ltd</publisher><subject>Alkanes ; Communication ; Communications ; computation ; Computer applications ; Crystal lattices ; Crystals ; C−H activation ; Environments ; Low temperature ; Mathematical analysis ; Molecular dynamics ; Molecular structure ; Pentane ; Rhodium ; sigma complexes ; Single crystals ; Solid state ; Spectroscopy ; Temperature effects ; X-ray diffraction</subject><ispartof>Angewandte Chemie International Edition, 2016-03, Vol.55 (11), p.3677-3681</ispartof><rights>2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.</rights><rights>2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><rights>2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c7079-6f75cb1a3b4dc9f475e8f8f8104b039096dff80c708c232bb5e7a29191be40b73</citedby><cites>FETCH-LOGICAL-c7079-6f75cb1a3b4dc9f475e8f8f8104b039096dff80c708c232bb5e7a29191be40b73</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fanie.201511269$$EPDF$$P50$$Gwiley$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.201511269$$EHTML$$P50$$Gwiley$$Hfree_for_read</linktohtml><link.rule.ids>230,314,776,780,881,1411,27901,27902,45550,45551</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/26880330$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Chadwick, F. Mark</creatorcontrib><creatorcontrib>Rees, Nicholas H.</creatorcontrib><creatorcontrib>Weller, Andrew S.</creatorcontrib><creatorcontrib>Krämer, Tobias</creatorcontrib><creatorcontrib>Iannuzzi, Marcella</creatorcontrib><creatorcontrib>Macgregor, Stuart A.</creatorcontrib><title>A Rhodium-Pentane Sigma-Alkane Complex: Characterization in the Solid State by Experimental and Computational Techniques</title><title>Angewandte Chemie International Edition</title><addtitle>Angew. Chem. Int. Ed</addtitle><description>The pentane σ‐complex [Rh{Cy2P(CH2CH2)PCy2}(η2:η2‐C5H12)][BArF4] is synthesized by a solid/gas single‐crystal to single‐crystal transformation by addition of H2 to a precursor 1,3‐pentadiene complex. Characterization by low temperature single‐crystal X‐ray diffraction (150 K) and SSNMR spectroscopy (158 K) reveals coordination through two Rh⋅⋅⋅H−C interactions in the 2,4‐positions of the linear alkane. Periodic DFT calculations and molecular dynamics on the structure in the solid state provide insight into the experimentally observed Rh⋅⋅⋅H−C interaction, the extended environment in the crystal lattice and a temperature‐dependent pentane rearrangement implicated by the SSNMR data.
Pentane takes a walk: The pentane sigma complex [Rh{Cy2P(CH2CH2)PCy2}(η2:η2‐C5H12)][BArF4] can be synthesized by a solid/gas single‐crystal to single‐crystal transformation. Periodic DFT calculations, molecular dynamics, and NMR spectroscopy provided insights into the fluxional processes occurring in the solid state.</description><subject>Alkanes</subject><subject>Communication</subject><subject>Communications</subject><subject>computation</subject><subject>Computer applications</subject><subject>Crystal lattices</subject><subject>Crystals</subject><subject>C−H activation</subject><subject>Environments</subject><subject>Low temperature</subject><subject>Mathematical analysis</subject><subject>Molecular dynamics</subject><subject>Molecular structure</subject><subject>Pentane</subject><subject>Rhodium</subject><subject>sigma complexes</subject><subject>Single crystals</subject><subject>Solid state</subject><subject>Spectroscopy</subject><subject>Temperature effects</subject><subject>X-ray diffraction</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2016</creationdate><recordtype>article</recordtype><sourceid>24P</sourceid><recordid>eNqFkc9v0zAUxy0EYr-4ckSRuOyS4hcndswBqVRdmZjKRId2tOzEWbw5cYkTaPfX46yjGhxAPvjZ_ny_-j4_hF4DngDGyTvZGj1JMGQACeXP0CFkCcSEMfI81CkhMcszOEBH3t8GPs8xfYkOEhoKQvAh2kyjr7UrzdDEl7rtZaujlblpZDy1d-Nh5pq11Zv30ayWnSx63Zl72RvXRqaN-jrQzpoyWvWy15HaRvPNOiDNaGUj2ZYPBkP_IAk3V7qoW_N90P4Evaik9frV436Mvp3Nr2af4osvi_PZ9CIuGGY8phXLCgWSqLQseJWyTOdVWIBThQnHnJZVleMA50VCEqUyzWTCgYPSKVaMHKMPO9_1oBpdFiFZJ61Yh5Cy2wonjfjzpTW1uHE_RMo4C67B4PTRoHNj8F40xhfa2vA9bvACGOU8JwxDQN_-hd66oQt9B4pjSimw5N8UozkFIGTMPdlRRee873S1jwxYjKMX4-jFfvRB8OZpo3v896wDwHfAT2P19j92Yro8nz81j3da43u92WtldycoIywT18uF-Li6XiwX2WexIr8A2kLK4g</recordid><startdate>20160307</startdate><enddate>20160307</enddate><creator>Chadwick, F. Mark</creator><creator>Rees, Nicholas H.</creator><creator>Weller, Andrew S.</creator><creator>Krämer, Tobias</creator><creator>Iannuzzi, Marcella</creator><creator>Macgregor, Stuart A.</creator><general>Blackwell Publishing Ltd</general><general>Wiley Subscription Services, Inc</general><general>John Wiley and Sons Inc</general><scope>BSCLL</scope><scope>24P</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><scope>5PM</scope></search><sort><creationdate>20160307</creationdate><title>A Rhodium-Pentane Sigma-Alkane Complex: Characterization in the Solid State by Experimental and Computational Techniques</title><author>Chadwick, F. Mark ; Rees, Nicholas H. ; Weller, Andrew S. ; Krämer, Tobias ; Iannuzzi, Marcella ; Macgregor, Stuart A.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c7079-6f75cb1a3b4dc9f475e8f8f8104b039096dff80c708c232bb5e7a29191be40b73</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2016</creationdate><topic>Alkanes</topic><topic>Communication</topic><topic>Communications</topic><topic>computation</topic><topic>Computer applications</topic><topic>Crystal lattices</topic><topic>Crystals</topic><topic>C−H activation</topic><topic>Environments</topic><topic>Low temperature</topic><topic>Mathematical analysis</topic><topic>Molecular dynamics</topic><topic>Molecular structure</topic><topic>Pentane</topic><topic>Rhodium</topic><topic>sigma complexes</topic><topic>Single crystals</topic><topic>Solid state</topic><topic>Spectroscopy</topic><topic>Temperature effects</topic><topic>X-ray diffraction</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Chadwick, F. Mark</creatorcontrib><creatorcontrib>Rees, Nicholas H.</creatorcontrib><creatorcontrib>Weller, Andrew S.</creatorcontrib><creatorcontrib>Krämer, Tobias</creatorcontrib><creatorcontrib>Iannuzzi, Marcella</creatorcontrib><creatorcontrib>Macgregor, Stuart A.</creatorcontrib><collection>Istex</collection><collection>Wiley Online Library Open Access</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Chadwick, F. Mark</au><au>Rees, Nicholas H.</au><au>Weller, Andrew S.</au><au>Krämer, Tobias</au><au>Iannuzzi, Marcella</au><au>Macgregor, Stuart A.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>A Rhodium-Pentane Sigma-Alkane Complex: Characterization in the Solid State by Experimental and Computational Techniques</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew. Chem. Int. Ed</addtitle><date>2016-03-07</date><risdate>2016</risdate><volume>55</volume><issue>11</issue><spage>3677</spage><epage>3681</epage><pages>3677-3681</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><coden>ACIEAY</coden><abstract>The pentane σ‐complex [Rh{Cy2P(CH2CH2)PCy2}(η2:η2‐C5H12)][BArF4] is synthesized by a solid/gas single‐crystal to single‐crystal transformation by addition of H2 to a precursor 1,3‐pentadiene complex. Characterization by low temperature single‐crystal X‐ray diffraction (150 K) and SSNMR spectroscopy (158 K) reveals coordination through two Rh⋅⋅⋅H−C interactions in the 2,4‐positions of the linear alkane. Periodic DFT calculations and molecular dynamics on the structure in the solid state provide insight into the experimentally observed Rh⋅⋅⋅H−C interaction, the extended environment in the crystal lattice and a temperature‐dependent pentane rearrangement implicated by the SSNMR data.
Pentane takes a walk: The pentane sigma complex [Rh{Cy2P(CH2CH2)PCy2}(η2:η2‐C5H12)][BArF4] can be synthesized by a solid/gas single‐crystal to single‐crystal transformation. Periodic DFT calculations, molecular dynamics, and NMR spectroscopy provided insights into the fluxional processes occurring in the solid state.</abstract><cop>Germany</cop><pub>Blackwell Publishing Ltd</pub><pmid>26880330</pmid><doi>10.1002/anie.201511269</doi><tpages>5</tpages><edition>International ed. in English</edition><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1433-7851 |
| ispartof | Angewandte Chemie International Edition, 2016-03, Vol.55 (11), p.3677-3681 |
| issn | 1433-7851 1521-3773 |
| language | eng |
| recordid | cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_4797708 |
| source | Wiley Online Library - AutoHoldings Journals |
| subjects | Alkanes Communication Communications computation Computer applications Crystal lattices Crystals C−H activation Environments Low temperature Mathematical analysis Molecular dynamics Molecular structure Pentane Rhodium sigma complexes Single crystals Solid state Spectroscopy Temperature effects X-ray diffraction |
| title | A Rhodium-Pentane Sigma-Alkane Complex: Characterization in the Solid State by Experimental and Computational Techniques |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-02-21T18%3A23%3A26IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_pubme&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=A%20Rhodium-Pentane%20Sigma-Alkane%20Complex:%20Characterization%20in%20the%20Solid%20State%20by%20Experimental%20and%20Computational%20Techniques&rft.jtitle=Angewandte%20Chemie%20International%20Edition&rft.au=Chadwick,%20F.%20Mark&rft.date=2016-03-07&rft.volume=55&rft.issue=11&rft.spage=3677&rft.epage=3681&rft.pages=3677-3681&rft.issn=1433-7851&rft.eissn=1521-3773&rft.coden=ACIEAY&rft_id=info:doi/10.1002/anie.201511269&rft_dat=%3Cproquest_pubme%3E3966533681%3C/proquest_pubme%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=1768611337&rft_id=info:pmid/26880330&rfr_iscdi=true |