4848-43-5Relevant articles and documents
A One-Step Preparation of Tetradentate Ligands with Nitrogen and Phosphorus Donors by Reductive Amination and Representative Iron Complexes
Gradiski, Matthew V.,Kharat, Ali Nemati,Lough, Alan J.,Morris, Robert H.,Ong, Maegan S. E.,Smith, Samantha A. M.
, (2020)
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.
Method for conducting catalytic hydrogenation on nitrogen-containing unsaturated heterocyclic compound
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Paragraph 0071; 0077-0079, (2020/01/03)
The invention provides a method for conducting catalytic hydrogenation on a nitrogen-containing unsaturated heterocyclic compound, and belongs to the technical field of catalytic hydrogenation. The provided method for conducting catalytic hydrogenation on the nitrogen-containing unsaturated heterocyclic compound comprises the following step: in the presence of hydrogen and a manganese catalyst, with the nitrogen-containing unsaturated heterocyclic compound as a substrate, carrying out a hydrogenation reaction. According to the method for conducting catalytic hydrogenation on the nitrogen-containing unsaturated heterocyclic compound, he adopted manganese catalyst is an NNP-type pincer manganese catalyst, has the advantages of being cheap, easy to obtain and low in toxicity compared with noble metal catalysts, has the advantages of being wide in substrate applicability and high in target product yield compared with an existing cheap metal iron catalyst or cobalt catalyst, and is higher in electron donating ability and smaller in steric hindrance compared with a PNP-type pincer manganese catalyst, and thus shows higher reaction activity in a series of hydrogenation reactions, and thetarget product yield is up to 99%.
Photosensitive iron(II)-based CO-releasing molecules (CORMs) with vicinal amino and diphenylphosphino substituted chelating ligands
Jazzazi, Taghreed M.A.,G?rls, Helmar,Gessner, Guido,Heinemann, Stefan H.,Westerhausen
, p. 63 - 70 (2013/06/04)
The reactions of [Fe(H2O)6] [BF4] 2 with aminoethyl-diphenylphosphane and 2-(diphenylphosphino)aniline lead to the formation of trans-[Fe(NC-Me)2(H2NCH 2CH2PPh2)2] [BF4] 2 (1a) and trans-[Fe(NC-Me)2(H2NC 6H4-2-PPh2)2] [BF4] 2 (1b), respectively. One acetonitrile ligand can be substituted by CO yielding [Fe(CO)(NC-Me)(H2NCH2CH2PPh 2)2] [BF4]2 (2a, CORM-P1) and [Fe(CO)(NC-Me)(H2NC6H4-2-PPh2) 2] [BF4]2 (2b, CORM-P2). Upon irradiation with visible light, CO is liberated making especially 2a a promising photo-CORM whereas for 2b a slow and incomplete CO release is observed.
