@article { ISI:000384404700030, title = {Low coordinate iron derivatives stabilized by a beta-diketiminate mimic. Synthesis and coordination chemistry of enamidophosphinimine scaffolds to generate diiron dinitrogen complexes}, journal = {DALTON TRANSACTIONS}, volume = {45}, number = {37}, year = {2016}, pages = {14697-14708}, abstract = {In an effort to mimic N-diaryl-beta-diketiminate ligands (Nacnac), we have converted N-arylimine phosphine ligands to enamine-phosphinimines via the Staudinger reaction. By varying the aryl azide, one can access enamine-phosphinimine ligands with the same or different N-aryl substituents on both the enamine and phosphinimine units, which allows this intrinsically unsymmetrical bidentate donor set to present variable steric effects at the metal center. The enamine-phosphinimine was deprotonated and used in metathetical reactions with Fe(II) bromide precursors to generate low coordinate complexes of the empirical formula {[}(NpNAr,Ar{\textquoteright})-Np-CY5]FeBr (where CY5 = cyclopentenyl; Ar,Ar{\textquoteright} = 2,6-diisopropylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl). Depending on the substituents, these bromide derivatives can be monomeric or dimeric via bromide bridges. Reduction under dinitrogen using potassium graphite generates the dinitrogen complexes ({[}(NpNAr,Ar{\textquoteright})-Np-CY5]Fe)(2)(mu-N-2) for Ar,Ar{\textquoteright} = 2,6-diisopropylphenyl, and Ar = 2,6-dimethylphenyl, Ar{\textquoteright} = 2,4,6-trimethylphenyl. However, for the former, a unsymmetrical side product can be isolated that has a bridging N-2,6-diisopropylphenylimide unit with one enamido-phosphine ligand bound to one iron and the other iron stabilized with an intact enamido-phosphinimine. When the steric bulk is reduced on both nitrogen donors, a complicated product mixture is obtained after reduction from which a small amount of {[}(NpNAr,Ar{\textquoteright})-Np-CY5]Fe{[}(NPAr)-N-CY5] (Ar,Ar{\textquoteright} = 2,6-dimethylphenyl) could be isolated. All of these complexes are paramagnetic and have been characterized by elemental analysis, magnetic studies and X-ray crystallography.}, issn = {1477-9226}, doi = {10.1039/c6dt01673a}, author = {Hein, Nicholas M. and Suzuki, Tatsuya and Ogawa, Takahiko and Fryzuk, Michael D.} }