Ligand cleavage put into reverse: P--C bond breaking and remaking in an alkylphosphane iron complex

Chemistry : a European Journal
Stephan W KohlAndreas Grohmann

Abstract

Complex formation between FeX(2)6 H(2)O (X=BF(4) or ClO(4)) and the pyridine-derived tetrapodal tetraphosphane C(5)H(3)N[CMe(CH(2)PMe(2))(2)](2) (1) in methanol proceeds with solvent-induced cleavage of one PMe(2) group. Depending on the reaction temperature and the nature of the counterion, iron(II) is coordinated, in distorted square-pyramidal fashion, by the anionic remainder of the chelating ligand, C(5)H(3)N[CMe(CH(2)PMe(2))(2)][CMe(CH(2)PMe(2))(CH(2) (-))] (NP(3)C(-) donor set: X=BF(4), -50 degrees C: 2; X=ClO(4), RT: 4) or its protonated form C(5)H(3)N[CMe(CH(2)PMe(2))(2)][CMe(CH(2)PMe(2))(CH(3))], in which the methyl group is in agostic interaction with the metal centre (X=BF(4), RT: 3; X=ClO(4), +50 degrees C: 5). A monodentate phosphinite ligand Me(2)POMe, formed from the cleaved PMe(2) group and methanol, completes the coordination octahedron in both cases. Working in CD(3)OD (X=BF(4), RT) gives the deuterium-substituted analogue of 3, with ligands L(CH(2)D) (L=residual chelating ligand) and Me(2)POCD(3). A mechanism for the observed phosphorus-carbon bond cleavage is suggested. Complex 2, when isolated at -50 degrees C, is stable in the solid state even at room temperature. The reaction of 2 in methanol with carbon ...Continue Reading

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Citations

Jan 18, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Stephan W KohlAndreas Grohmann
Jun 30, 2007·Angewandte Chemie·Neal P MankadJonas C Peters
Apr 11, 2009·Chemistry : a European Journal·Nils MeyerRobert H Morris
May 8, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Javier RuizMarta E G Mosquera
Sep 13, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Javier RuizRoberto Quesada
Oct 21, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Christopher W TateNicholas J Long
Jan 28, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Andreas Grohmann
Oct 30, 2010·Inorganic Chemistry·Jeremy M Smith, Jeffrey R Long
Jun 2, 2011·Journal of the American Chemical Society·Paraskevi O LagaditisRobert H Morris

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