An anionic phosphenium complex as an ambident nucleophile
A unique anionic phosphenium complex was prepared from reaction of an N-heterocyclic chlorophosphine with Collman's reagent or K[HFe(CO)4]/NaH and characterized by spectral and XRD data. The complex behaves as an ambident nucleophile. Reactions with acetic acid, ClSnPh3, and a further equivalen...
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| Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2015-04, Vol.44 (13), p.6023-6031 |
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| container_issue | 13 |
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| container_title | Dalton transactions : an international journal of inorganic chemistry |
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| creator | Stadelmann, B Bender, J Förster, D Frey, W Nieger, M Gudat, D |
| description | A unique anionic phosphenium complex was prepared from reaction of an N-heterocyclic chlorophosphine with Collman's reagent or K[HFe(CO)4]/NaH and characterized by spectral and XRD data. The complex behaves as an ambident nucleophile. Reactions with acetic acid, ClSnPh3, and a further equivalent of an N-heterocyclic chlorophosphine proceed via electrophilic functionalization at the metal site to yield appropriate mono- or bis-phosphenium complexes. Reaction with MeI at -70 °C produces a P-alkylation product as the first spectroscopically detectable intermediate, which decays at a higher temperature to give a mixture of free P-methylated N-heterocyclic phosphine and its Fe(CO)4 complex. The different reaction products were characterized by spectral and XRD data. Computational studies indicate that the NHP units in all complexes display π-acceptor behaviour but show no disposition to adopt phosphide-like character or formally oxidize the metal centre. |
| doi_str_mv | 10.1039/c5dt00008d |
| format | Article |
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The complex behaves as an ambident nucleophile. Reactions with acetic acid, ClSnPh3, and a further equivalent of an N-heterocyclic chlorophosphine proceed via electrophilic functionalization at the metal site to yield appropriate mono- or bis-phosphenium complexes. Reaction with MeI at -70 °C produces a P-alkylation product as the first spectroscopically detectable intermediate, which decays at a higher temperature to give a mixture of free P-methylated N-heterocyclic phosphine and its Fe(CO)4 complex. The different reaction products were characterized by spectral and XRD data. 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Computational studies indicate that the NHP units in all complexes display π-acceptor behaviour but show no disposition to adopt phosphide-like character or formally oxidize the metal centre.</description><subject>Acetic acid</subject><subject>Computation</subject><subject>Decay</subject><subject>Equivalence</subject><subject>Nucleophiles</subject><subject>Phosphines</subject><subject>Spectra</subject><subject>Spectroscopy</subject><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><recordid>eNqFkEtLw0AUhQdRbK1u_AGSpQjReWeyLKkvKLip6zCZuaEjyUzMJKD_3tTWbr2be-B8nMWH0DXB9wSz_MEIO-DplD1Bc8KzLM0p46fHTOUMXcT4gTGlWNBzNKMimyJnc5QvfaK9C96ZpNuG2G3Bu7FNTGi7Br4SHac60W3lLPgh8aNpIHRb18AlOqt1E-Hq8Bfo_elxU7yk67fn12K5Tg0TckhpRWuV5wQwI5opWteY8cqANgqYAYsFVlhwbLRUWlqpSaWtVWCMUFIAYwt0u9_t-vA5QhzK1kUDTaM9hDGWJONc5jmj_H9UysmIIGq3erdHTR9i7KEuu961uv8uCS53VstCrDa_VlcTfHPYHasW7BH908h-AKWocXY</recordid><startdate>20150407</startdate><enddate>20150407</enddate><creator>Stadelmann, B</creator><creator>Bender, J</creator><creator>Förster, D</creator><creator>Frey, W</creator><creator>Nieger, M</creator><creator>Gudat, D</creator><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope></search><sort><creationdate>20150407</creationdate><title>An anionic phosphenium complex as an ambident nucleophile</title><author>Stadelmann, B ; Bender, J ; Förster, D ; Frey, W ; Nieger, M ; Gudat, D</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c356t-2b2f8991e031a382ff034bceac8e3ced05080540ca68a6d6a1badd8ecc5865e33</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><topic>Acetic acid</topic><topic>Computation</topic><topic>Decay</topic><topic>Equivalence</topic><topic>Nucleophiles</topic><topic>Phosphines</topic><topic>Spectra</topic><topic>Spectroscopy</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Stadelmann, B</creatorcontrib><creatorcontrib>Bender, J</creatorcontrib><creatorcontrib>Förster, D</creatorcontrib><creatorcontrib>Frey, W</creatorcontrib><creatorcontrib>Nieger, M</creatorcontrib><creatorcontrib>Gudat, D</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Stadelmann, B</au><au>Bender, J</au><au>Förster, D</au><au>Frey, W</au><au>Nieger, M</au><au>Gudat, D</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>An anionic phosphenium complex as an ambident nucleophile</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><addtitle>Dalton Trans</addtitle><date>2015-04-07</date><risdate>2015</risdate><volume>44</volume><issue>13</issue><spage>6023</spage><epage>6031</epage><pages>6023-6031</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>A unique anionic phosphenium complex was prepared from reaction of an N-heterocyclic chlorophosphine with Collman's reagent or K[HFe(CO)4]/NaH and characterized by spectral and XRD data. 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| ispartof | Dalton transactions : an international journal of inorganic chemistry, 2015-04, Vol.44 (13), p.6023-6031 |
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| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Acetic acid Computation Decay Equivalence Nucleophiles Phosphines Spectra Spectroscopy |
| title | An anionic phosphenium complex as an ambident nucleophile |
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