A One-Step Preparation of Tetradentate Ligands with Nitrogen and Phosphorus Donors by Reductive Amination and Representative Iron Complexes

This is the accepted article.The synthesis and use of the first examples of unsymmetrical, mixed phosphine donor tripodal NPP’2 ligands N(CH2CH2PR2)2(CH2CH2PPh2) are presented. The ligands are synthesized via a convenient, one pot reductive amination using 2-(diphenylphosphino)ethylamine and various substituted phosphonium dimers in order to introduce mixed phosphine donors substituted with P/P’ being Ph/Cy (2), Ph/iPr (3), Ph/iBu (4), Ph/o-Tol (5), and Ph/p-Tol (6). Additionally, we have developed the first known synthesis of a symmetrical tripodal NP3 ligand N(CH2CH2PiBu2)3 using bench safe ammonium acetate as the lone nitrogen source (7). This new protocol eliminates the use of extremely dangerous nitrogen mustard reagents typically required to synthesize NP3 ligands. Some of these tetradentate ligands and also P2NN’ ligands N(CH2-o-C5H4N)(CH2CH2PR2)2 (P2NN’-Cy, R = Cy; P2NN’-Ph, R = Ph) prepared by reductive amination using 2-picolylamine, are used in the synthesis and reactions of iron complexes. FeCl2(P2NN’-Cy) (8) undergoes single halide abstraction with NaBPh4 to give the trigonal bipyramidal complex [FeCl(P2NN’-Cy)][BPh4] (9). Upon exposure to CO(g), complex 9 readily coordinates CO giving [FeCl(P2NN’-Cy)(CO)][BPh4] (10) and further treatment with an excess of NaBH4 results in formation of the hydride complex [Fe(H)(P2NN’-Cy)(CO)][BPh4] (11). Our previously reported complex FeCl2(P2NN’-Ph) undergoes double halide abstraction with NaBPh4 in the presence of he coordinating solvent to give [Fe(NCMe)2(P2NN’-Ph)][BPh4]2 (12). Ligand 3 can be coordinated to FeCl2 and upon sequential halide abstraction, treatment with NaBH4, and exposure to an atmosphere of dinitrogen, the dinitrogen hydride complex [Fe(H)(NPP’2-iPr)(N2)][BPh4] (13) is isolated. Our symmetrical NP3 ligand 7 can also be coordinated to FeCl2 and upon exposure to an atmosphere of CO(g), selectively forms [FeCl(NP3)(CO)][BPh4] (14) after salt metathesis with NaBPh4. Complex 14 can be treated with an excess of NaBH4 to give the hydride complex [Fe(H)(NP3)(CO)][BPh4] (15) which can further be deprotonated/reduced to the Fe(0) complex Fe(NP3)(CO) (16) upon treatment with an excess of KH.NSERC is acknowledged for a Discovery Grant to R. H. M. and the Strategic Grant “Catalytic Synthesis of Specialty Chemicals from Sustainable Resources.” The Ontario Government is acknowledged for an Ontario Graduate Scholarship for M. V. G