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

Matthew V Gradiski; Ali Nemati Kharat; Maegan S E Ong; Alan J Lough; Samantha A M Smith; Robert H Morris

doi:10.1021/acs.inorgchem.0c01535

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

Inorg Chem. 2020 Aug 3;59(15):11041-11053. doi: 10.1021/acs.inorgchem.0c01535. Epub 2020 Jul 20.

Authors

Matthew V Gradiski¹, Ali Nemati Kharat², Maegan S E Ong¹, Alan J Lough¹, Samantha A M Smith¹, Robert H Morris¹

Affiliations

¹ Department of Chemistry, University of Toronto, 80 Saint George St., Toronto, Ontario, Canada, M5S 3H6.
² School of Chemistry, College of Science, University of Tehran, Tehran, Iran.

PMID: 32687329
DOI: 10.1021/acs.inorgchem.0c01535

Abstract

The synthesis and use of the first examples of unsymmetrical, mixed phosphine donor tripodal NPP₂' 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', those 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 the 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)(NPP₂'-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.