title: Nitrogen-ligated iron complexes: photolytic approach to the FeN+ moiety.
abstract: The synthesis of (PNP)FeCl, (PNP)Fe[NH(xylyl)], and (PNP)FeN3 are reported(PNP = (tBu2PCH2SiMe2)2N-). While the azide is thermally stable, it is photosensitive to lose N2 and form [(PNPN)Fe]2,in which the nitride ligand has formed a double bond to one phosphorus, and this N bridges to a second iron to form a 2-fold symmetric dimer. The reaction energy to form the (undetected) monomeric [eta3- tBu2PCH2SiMe2NSiMe2CH2PtBu2N]Fe is -15.9 kcal/mol, so this PIII --> PV oxidation is favorable. The eta2 version of this same species is less stable by 23.7 kcal/mol, which shows that the loss of one P--> Fe bond is caused by dimerization, and therefore, it does not precede and cause dimerization. A comparison is made to Ru analogs.
authors.affiliation: Department of Chemistry, Indiana University, Bloomington, Indiana 47405, USA.
authors.forename: Drew
authors.initials: D
authors.lastname: Buschhorn
authors.forename: Maren
authors.initials: M
authors.lastname: Pink
authors.forename: Hongjun
authors.initials: H
authors.lastname: Fan
authors.forename: Kenneth G
authors.initials: KG
authors.lastname: Caulton