Synthesis of a Stable Compound with Fivefold Bonding Between Two Chromium(I) Centers
Although in principle transition metals can form bonds with six shared electron pairs, only quadruply bonded compounds can be isolated as stable species at room temperature. Here we show that the reduction of {Cr([micro]-Cl)Ar'}₂ [where Ar' indicates C₆H₃-2,6(C₆H₃-2,6-Pr[superscript i]₂)₂...
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| Veröffentlicht in: | Science (American Association for the Advancement of Science) 2005-11, Vol.310 (5749), p.844-847 |
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| creator | Nguyen, Tailuan Sutton, Andrew D Brynda, Marcin Fettinger, James C Long, Gary J Power, Philip P |
| description | Although in principle transition metals can form bonds with six shared electron pairs, only quadruply bonded compounds can be isolated as stable species at room temperature. Here we show that the reduction of {Cr([micro]-Cl)Ar'}₂ [where Ar' indicates C₆H₃-2,6(C₆H₃-2,6-Pr[superscript i]₂)₂ and Pr indicates isopropyl] with a slight excess of potassium graphite has produced a stable compound with fivefold chromium-chromium (Cr-Cr) bonding. The very air- and moisture-sensitive dark red crystals of Ar'CrCrAr' were isolated with greater than 40% yield. X-ray diffraction revealed a Cr-Cr bond length of 1.8351(4) angstroms (where the number in parentheses indicates the standard deviation) and a planar transbent core geometry. These data, the structure's temperature-independent paramagnetism, and computational studies support the sharing of five electron pairs in five bonding molecular orbitals between two 3d⁵ chromium(I) ions. |
| doi_str_mv | 10.1126/science.1116789 |
| format | Article |
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Here we show that the reduction of {Cr([micro]-Cl)Ar'}₂ [where Ar' indicates C₆H₃-2,6(C₆H₃-2,6-Pr[superscript i]₂)₂ and Pr indicates isopropyl] with a slight excess of potassium graphite has produced a stable compound with fivefold chromium-chromium (Cr-Cr) bonding. The very air- and moisture-sensitive dark red crystals of Ar'CrCrAr' were isolated with greater than 40% yield. X-ray diffraction revealed a Cr-Cr bond length of 1.8351(4) angstroms (where the number in parentheses indicates the standard deviation) and a planar transbent core geometry. These data, the structure's temperature-independent paramagnetism, and computational studies support the sharing of five electron pairs in five bonding molecular orbitals between two 3d⁵ chromium(I) ions.</description><identifier>ISSN: 0036-8075</identifier><identifier>EISSN: 1095-9203</identifier><identifier>DOI: 10.1126/science.1116789</identifier><identifier>PMID: 16179432</identifier><identifier>CODEN: SCIEAS</identifier><language>eng</language><publisher>Washington, DC: American Association for the Advancement of Science</publisher><subject>Analysis ; Atoms ; Chemical bonding ; Chemical bonds ; Chemical synthesis ; Chromium compounds ; Climate ; Climate change ; Condensed matter: electronic structure, electrical, magnetic, and optical properties ; Condensed matter: structure, mechanical and thermal properties ; Crystals ; Degassing of metals ; Diffraction ; Electron density of states and band structure of crystalline solids ; Electron states ; Electrons ; Exact sciences and technology ; Geometry ; Ligands ; Metals ; Molecular orbitals ; Organic Chemistry ; Organic compounds ; Organometalloidal and organometallic compounds ; Oxidases ; Physics ; Polymers and organic compounds ; Structure ; Structure of solids and liquids; crystallography ; Structure of specific crystalline solids ; Time series ; Water vapor</subject><ispartof>Science (American Association for the Advancement of Science), 2005-11, Vol.310 (5749), p.844-847</ispartof><rights>Copyright 2005 American Association for the Advancement of Science</rights><rights>2006 INIST-CNRS</rights><rights>COPYRIGHT 2005 American Association for the Advancement of Science</rights><rights>Copyright American Association for the Advancement of Science Nov 4, 2005</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c712t-c8ed2376154175a1bcb77a9b3caeadd268b3be8505b6cbc8198abd0cc2779edd3</citedby><cites>FETCH-LOGICAL-c712t-c8ed2376154175a1bcb77a9b3caeadd268b3be8505b6cbc8198abd0cc2779edd3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.jstor.org/stable/pdf/3842763$$EPDF$$P50$$Gjstor$$H</linktopdf><linktohtml>$$Uhttps://www.jstor.org/stable/3842763$$EHTML$$P50$$Gjstor$$H</linktohtml><link.rule.ids>314,776,780,799,2871,2872,27901,27902,57992,58225</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=17241332$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/16179432$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Nguyen, Tailuan</creatorcontrib><creatorcontrib>Sutton, Andrew D</creatorcontrib><creatorcontrib>Brynda, Marcin</creatorcontrib><creatorcontrib>Fettinger, James C</creatorcontrib><creatorcontrib>Long, Gary J</creatorcontrib><creatorcontrib>Power, Philip P</creatorcontrib><title>Synthesis of a Stable Compound with Fivefold Bonding Between Two Chromium(I) Centers</title><title>Science (American Association for the Advancement of Science)</title><addtitle>Science</addtitle><description>Although in principle transition metals can form bonds with six shared electron pairs, only quadruply bonded compounds can be isolated as stable species at room temperature. Here we show that the reduction of {Cr([micro]-Cl)Ar'}₂ [where Ar' indicates C₆H₃-2,6(C₆H₃-2,6-Pr[superscript i]₂)₂ and Pr indicates isopropyl] with a slight excess of potassium graphite has produced a stable compound with fivefold chromium-chromium (Cr-Cr) bonding. The very air- and moisture-sensitive dark red crystals of Ar'CrCrAr' were isolated with greater than 40% yield. X-ray diffraction revealed a Cr-Cr bond length of 1.8351(4) angstroms (where the number in parentheses indicates the standard deviation) and a planar transbent core geometry. These data, the structure's temperature-independent paramagnetism, and computational studies support the sharing of five electron pairs in five bonding molecular orbitals between two 3d⁵ chromium(I) ions.</description><subject>Analysis</subject><subject>Atoms</subject><subject>Chemical bonding</subject><subject>Chemical bonds</subject><subject>Chemical synthesis</subject><subject>Chromium compounds</subject><subject>Climate</subject><subject>Climate change</subject><subject>Condensed matter: electronic structure, electrical, magnetic, and optical properties</subject><subject>Condensed matter: structure, mechanical and thermal properties</subject><subject>Crystals</subject><subject>Degassing of metals</subject><subject>Diffraction</subject><subject>Electron density of states and band structure of crystalline solids</subject><subject>Electron states</subject><subject>Electrons</subject><subject>Exact sciences and 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Here we show that the reduction of {Cr([micro]-Cl)Ar'}₂ [where Ar' indicates C₆H₃-2,6(C₆H₃-2,6-Pr[superscript i]₂)₂ and Pr indicates isopropyl] with a slight excess of potassium graphite has produced a stable compound with fivefold chromium-chromium (Cr-Cr) bonding. The very air- and moisture-sensitive dark red crystals of Ar'CrCrAr' were isolated with greater than 40% yield. X-ray diffraction revealed a Cr-Cr bond length of 1.8351(4) angstroms (where the number in parentheses indicates the standard deviation) and a planar transbent core geometry. These data, the structure's temperature-independent paramagnetism, and computational studies support the sharing of five electron pairs in five bonding molecular orbitals between two 3d⁵ chromium(I) ions.</abstract><cop>Washington, DC</cop><pub>American Association for the Advancement of Science</pub><pmid>16179432</pmid><doi>10.1126/science.1116789</doi><tpages>4</tpages><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
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| ispartof | Science (American Association for the Advancement of Science), 2005-11, Vol.310 (5749), p.844-847 |
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| source | American Association for the Advancement of Science; Jstor Complete Legacy |
| subjects | Analysis Atoms Chemical bonding Chemical bonds Chemical synthesis Chromium compounds Climate Climate change Condensed matter: electronic structure, electrical, magnetic, and optical properties Condensed matter: structure, mechanical and thermal properties Crystals Degassing of metals Diffraction Electron density of states and band structure of crystalline solids Electron states Electrons Exact sciences and technology Geometry Ligands Metals Molecular orbitals Organic Chemistry Organic compounds Organometalloidal and organometallic compounds Oxidases Physics Polymers and organic compounds Structure Structure of solids and liquids crystallography Structure of specific crystalline solids Time series Water vapor |
| title | Synthesis of a Stable Compound with Fivefold Bonding Between Two Chromium(I) Centers |
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