1346171-72-9

Upstream product

• 620-93-9 di-p-tolylamine 
• 40244-90-4 Chlorodiisopropylphosphane 
• 27996-13-0 α,α'-dibromo-di-p-tolylamine 

Downstream Products

• 1333235-55-4 C₃₂H₃₇NP₂ 
• 1346171-74-1 (CH₂)2(NCHC₆H₃(CH₃)NHC₆H₃(CH₃)P(CH(CH₃)2)2)2 
• 1346171-73-0 [(H)N(2-C(O)H-4-Me-C₆H₃)(2-P(iPr)2-4-Me-C₆H₃)] 

Relevant academic research and scientific papers

Unsymmetrical RPNPR′ pincer ligands and their group 10 complexes

Two new unsymmetrical RPNPR′-type pincer ligands based on a bis(tolyl)amine framework have been synthesized and characterized by a variety of techniques, including X-ray crystallography. These ligands have been coordinated to Ni, Pd, and Pt precursors to provide a number of well-characterized group 10 halides. Conversion of these metal halides to metal hydrides was accomplished using borohydride reagents, or by direct interaction of the ligand with the zerovalent metal precursor. The insertion of oxygen into these hydrides in an attempt to prepare metal hydroperoxides has been examined; however, we were unable to obtain stable and isolable hydroperoxide species. The Royal Society of Chemistry 2011.

Comparison of the electronic properties of diarylamido-based PNZ pincer ligands: Redox activity at the ligand and donor ability toward the metal

This paper presents the synthesis and characterization of a series of pincer ligands and their Ni, Pd, Pt, and Rh complexes. The ligands under examination are based on a diarylamine which is modified either by two phosphino (-PR2) substituents in the ortho-positions (PNP ligands) or by a combination of a phosphino and an iminyl (?CH - NX) substituent (PNN ligands). The ligands can be broken down into three groups: (a) C2v-symmetric PNP ligands with identical side ?PR2 donors, (b) Cs-symmetric PNP? ligands with different ?PR2 side donors, and (c) PNN ligands containing a ?PiPr2 side donor. All of the ligands under study readily formed square-planar complexes of the types (PNZ)PdCl, (PNZ)Pd(OAc), and (PNZ)RhCO, where PNZ is the corresponding anionic tridentate pincer ligand. For select PNP ligands, (PNP)NiCl and (PNP)PtCl were also studied. The (PNZ)MCl complexes (M = Ni, Pd, Pt) underwent quasireversible oxidation in cyclic voltammetry experiments. Based on the close similarity of formal potentials for Ni, Pd, and Pt analogs, and based on the previous literature evidence, these oxidation events are ascribed primarily to the PNZ ligand, and the E1/2 values can be used to compare the ease of oxidation of different ligands. A (PNP)PdCl complex containing methoxy substituents para- to the central nitrogen underwent two quasireversible oxidations. Two mono-oxidized complexes were isolated and structurally characterized in comparison to their neutral analog, revealing minimal changes in the bond distances and angles. Several other neutral complexes were also structurally characterized. The carbonyl stretching frequency in (PNZ)RhCO complexes was used to gauge the donating ability of the various pincer ligands toward the metal. Comparison of E1/2 values for (PNZ)PdCl and ?CO values for (PNZ)RhCO revealed that the two are not consistently correlated across all the studied ligands and can be tuned to different degrees through judicious ligand alteration.

Ligand survey results in identification of PNP pincer complexes of iridium as long-lived and chemoselective catalysts for dehydrogenative borylation of terminal alkynes

Following the report on the successful use of SiNN pincer complexes of iridium as catalysts for dehydrogenative borylation of terminal alkynes (DHBTA) to alkynylboronates, this work examined a wide variety of related pincer ligands in the supporting role in DHBTA. The ligand selection included both new and previously reported ligands and was developed to explore systematic changes to the SiNN framework (the 8-(2-diisopropylsilylphenyl)aminoquinoline). Surprisingly, only the diarylamido/bis(phosphine) PNP system showed any DHBTA reactivity. The specific PNP ligand (bearing two diisopropylphosphino side donors) used in the screen showed DHBTA activity inferior to SiNN. However, taking advantage of the ligand optimization opportunities presented by the PNP system via the changes in the substitution at phosphorus led to the discovery of a catalyst whose activity, longevity, and scope far exceeded that of the original SiNN archetype. Several Ir complexes were prepared in a model PNP system and evaluated as potential intermediates in the catalytic cycle. Among them, the (PNP)Ir diboryl complex and the borylvinylidene complex were shown to be less competent in catalysis and thus likely not part of the catalytic cycle.

Binuclear palladium complexes supported by bridged pincer ligands

A series of binucleating ligands each containing two tridentate pincer sites based on a central, monoanionic aryl (C) donor flanked by neutral phosphinito (P) and imino (N) donors, [(PCN)-(CH2)n-(PCN)] (1), or a central, monoanionic