Coordination chemistry of neutral mono-oxide, sulfide and selenide bis(diphenylphosphino)amine (DPPA)-based ligands and their N-substituted/functionalized derivatives

Abstract

This review provides a summary, including spectroscopic and structural data, of the metal complexes accessible with mono-oxide, sulfide and selenide bis(diphenylphosphino)amine (DPPA)-based ligands and their N-substituted/functionalized derivatives. The nature of the E (O, S ,Se) donor in these mixed P,P=E donor ligands strongly influences the nature of the resulting metal complexes, which can incorporate the DPPA-type ligand(s) as P-monodentate or P,E-chelate. When available, a comparison between the reactivity of the mixed P,P=E and parent P,P systems is given. The catalytic applications of P,E-supported metal complexes are also discussed.

Heteroleptic nickel complexes bearing O‐methyldithiophosphate and aminodiphosphine monosulfide ligands as robust molecular electrocatalysts for hydrogen evolution

“…In II A , the RN(PPh 2 ) ({S}PPh 2 ) only as a monodentate ligand coordinates to the nickel center by the stronger phosphorus atom from the Ph 2 P moiety instead of the sulfur atom in the Ph 2 P S one. [43,45] One (CH 3 O) 2 P{S}S À is monodentate ligand in II A while another (CH 3 O) 2 P{S}S À serves as bidentate one, [47] which is significantly different from the pentacoordinated intermediate containing the symmetric diphorsphine [33] or the aminodiphosphine ligand. [40] Subsequently, the intermediate II A is rapidly isomerized into ionic intermediate II B by the nucleophilic attack of the sulfur atom of the monodentate RN(PPh 2 )({S}PPh 2 ) ligand and the synergistic elimination of the monodentate (RO) 2 P{S}S À ligand, which is most likely due to the sterically crowded hindrance among the ligands in the intermediate II A.…”

“…Furthermore, particularly, both the five-membered chelate ring and/or the P,P S donor set and the nature of the N-substituent influence the catalytic performances of the metal complexes. [43][44][45] However, the heteroletic nickel complexes containing O-alkyldithiophosphate and aminodiphosphine monosulfide ligands as catalysts for hydrogen evolution are still unexplored. Interestingly, in these complexes, the nickel atom would be in a S 3 P coordination environment from the heterobidentate (the P,P S donor for aminodiphosphine monosulfide) and homobidentate (the S,S donor for O-alkyldithio-phosphate) ligands, which may have important effect on the catalytic performances of the complexes.…”

Multistimuli-responsive multicolor solid-state luminescence tuned by NH-dependent switchable hydrogen bonds

“…Both bis(diphenylphosphine) amine (dppa) and 5-tert-butyl-3-(2′-pyrimidinyl)-1H-1,2,4-triazole (bpmtzH) feature an N-H functional group that readily yields hydrogen bonding with neighbouring solvent molecules and counter-ions. 26,[34][35][36][37][38][39] Hence, it is feasible to construct multistimuli-responsive luminescent materials of Cu(I) complexes by using hydrogen bonding with those two distinct N-H groups from dppa and bpmtzH, since the forming and breaking of hydrogen bonding with those two different N-H groups affect the HOMO and LUMO energy levels to varying degrees.…”

Tetracarbonyl group 6B metal complexes of a N-(4-acetylphenyl)-N-(diphenylphosphino)amine ligand. Molecular structure of cis-[Cr(CO)4{4-CH3CO–C6H4-1-N(PPh2)2}]

“…These ligands are also used as assembling ligands for the formation of multinuclear complexes, due to the multiple donor atoms [ 13 ], and some of them and their derivatives have also found applications in surface and materials sciences [ 14 , 15 ]. Moreover, the chalcogenide forms of this type of ligands are also becoming increasingly important in view of their potential applications in catalysis [ 16 ].…”