{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T14:56:42Z","timestamp":1760367402295,"version":"build-2065373602"},"reference-count":20,"publisher":"Wiley","issue":"16","license":[{"start":{"date-parts":[[2006,3,10]],"date-time":"2006-03-10T00:00:00Z","timestamp":1141948800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2006,5,24]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Complex formation between FeX<jats:sub>2<\/jats:sub>\u22c56\u2009H<jats:sub>2<\/jats:sub>O (X=BF<jats:sub>4<\/jats:sub> or ClO<jats:sub>4<\/jats:sub>) and the pyridine\u2010derived tetrapodal tetraphosphane C<jats:sub>5<\/jats:sub>H<jats:sub>3<\/jats:sub>N[CMe(CH<jats:sub>2<\/jats:sub>PMe<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>]<jats:sub>2<\/jats:sub> (<jats:bold>1<\/jats:bold>) in methanol proceeds with solvent\u2010induced cleavage of one PMe<jats:sub>2<\/jats:sub> group. Depending on the reaction temperature and the nature of the counterion, iron(<jats:sc>II<\/jats:sc>) is coordinated, in distorted square\u2010pyramidal fashion, by the anionic remainder of the chelating ligand, C<jats:sub>5<\/jats:sub>H<jats:sub>3<\/jats:sub><jats:italic>N<\/jats:italic>[CMe(CH<jats:sub>2<\/jats:sub><jats:italic>P<\/jats:italic>Me<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>][CMe(CH<jats:sub>2<\/jats:sub><jats:italic>P<\/jats:italic>Me<jats:sub>2<\/jats:sub>)(<jats:italic>C<\/jats:italic>H<jats:sub>2<\/jats:sub><jats:sup>\u2212<\/jats:sup>)] (NP<jats:sub>3<\/jats:sub>C<jats:sup>\u2212<\/jats:sup> donor set: X=BF<jats:sub>4<\/jats:sub>, \u221250\u2009\u00b0C: <jats:bold>2<\/jats:bold>; X=ClO<jats:sub>4<\/jats:sub>, RT: <jats:bold>4<\/jats:bold>) or its protonated form C<jats:sub>5<\/jats:sub>H<jats:sub>3<\/jats:sub><jats:italic>N<\/jats:italic>[CMe(CH<jats:sub>2<\/jats:sub><jats:italic>P<\/jats:italic>Me<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>][CMe(CH<jats:sub>2<\/jats:sub><jats:italic>P<\/jats:italic>Me<jats:sub>2<\/jats:sub>)(<jats:italic>CH<jats:sub>3<\/jats:sub><\/jats:italic>)], in which the methyl group is in agostic interaction with the metal centre (X=BF<jats:sub>4<\/jats:sub>, RT: <jats:bold>3<\/jats:bold>; X=ClO<jats:sub>4<\/jats:sub>, +50\u2009\u00b0C: <jats:bold>5<\/jats:bold>). A monodentate phosphinite ligand Me<jats:sub>2<\/jats:sub>POMe, formed from the cleaved PMe<jats:sub>2<\/jats:sub> group and methanol, completes the coordination octahedron in both cases. Working in CD<jats:sub>3<\/jats:sub>OD (X=BF<jats:sub>4<\/jats:sub>, RT) gives the deuterium\u2010substituted analogue of <jats:bold>3<\/jats:bold>, with ligands L(CH<jats:sub>2<\/jats:sub>D) (L=residual chelating ligand) and Me<jats:sub>2<\/jats:sub>POCD<jats:sub>3<\/jats:sub>. A mechanism for the observed phosphorus\u2013carbon bond cleavage is suggested. Complex <jats:bold>2<\/jats:bold>, when isolated at \u221250\u2009\u00b0C, is stable in the solid state even at room temperature. The reaction of <jats:bold>2<\/jats:bold> in methanol with carbon monoxide (10.5 bar) at elevated temperature forms, in addition to as yet unidentified side products, the carbonyl complex [(<jats:bold>1<\/jats:bold>)Fe(CO)](BF<jats:sub>4<\/jats:sub>)<jats:sub>2<\/jats:sub> (<jats:bold>7<\/jats:bold>), in which the previous P\uf8ffC bond cleavage has been reversed, reforming the original tetrapodal pentadentate NP<jats:sub>4<\/jats:sub> ligand <jats:bold>1<\/jats:bold>. All compounds have been fully characterised, including X\u2010ray structure analyses in most cases.<\/jats:p>","DOI":"10.1002\/chem.200501577","type":"journal-article","created":{"date-parts":[[2006,3,10]],"date-time":"2006-03-10T06:47:20Z","timestamp":1141973240000},"page":"4313-4320","source":"Crossref","is-referenced-by-count":25,"title":["Ligand Cleavage Put into Reverse: P\uf8ffC Bond Breaking and Remaking in an Alkylphosphane Iron Complex"],"prefix":"10.1002","volume":"12","author":[{"given":"Stephan W.","family":"Kohl","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Frank W.","family":"Heinemann","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Markus","family":"Hummert","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Walter","family":"Bauer","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Andreas","family":"Grohmann","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2006,5,17]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"volume-title":"Applied Homogeneous Catalysis with Organometallic Compounds Vol. 1","year":"1996","key":"e_1_2_6_2_2"},{"volume-title":"Homogeneous Catalysis","year":"1992","author":"Parshall G. 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