66534-96-1

Upstream product

• 4848-43-5 (2-aminoethyl)diphenylphosphane 
• 829-85-6 diphenylphosphane 
• 821-48-7 bis-(2-chloroethyl)amine hydrochloride 
• 65567-06-8 lithium diphenylphosphide 
• 1079-66-9 chloro-diphenylphosphine 
• 66534-97-2 bis(2-(diphenylphosphino)ethyl)amine hydrochloride 

Downstream Products

• 114835-97-1 trichloro(bis(diphenylphosphinoethyl)amine)ruthenium(III) 
• 876407-60-2 CrCl₂((Ph₂PCH₂CH₂)2NH) 
• 1295649-40-9 [carbonylchlorohydrido{bis[2-(diphenylphosphinomethyl)ethyl]amino}ethylamino] ruthenium(II) 

Relevant academic research and scientific papers

Ruthenium-catalyzed ester reductions applied to pharmaceutical intermediates

Ruthenium pincer complexes were synthesized and used for catalytic ester reductions under mild conditions (～5 bar of hydrogen). An experimental design approach was used to optimize the conditions for yield, purity, and robustness. Evidence for the catalytically active ruthenium dihydride species is presented. Observed intermediates and side products, as well as time-course data, were used to build mechanistic insight. The optimized procedure was further demonstrated through scaled-up reductions of two pharmaceutically relevant esters, both in batch and continuous flow.

Catalytic Disproportionation of Formic Acid to Methanol by using Recyclable Silylformates

A novel strategy to prepare methanol from formic acid without an external reductant is presented. The overall process described herein consists of the disproportionation of silyl formates to methoxysilanes, catalyzed by ruthenium complexes, and the production of methanol by simple hydrolysis. Aqueous solutions of MeOH (>1 mL, >70 percent yield) were prepared in this manner. The sustainability of the reaction has been established by recycling of the silicon-containing by-products with inexpensive, readily available, and environmentally benign reagents.

Ruthenium-Pincer-Catalyzed Hydrogenation of Lactams to Amino Alcohols

By using the commercially available ruthenium pincer complex (Ru-MACHO-BH) as a catalyst, the challenging direct hydrogenation of lactams and analogues has been successfully accomplished to deliver corresponding value-added amino alcohols in good-to-excellent yields under mild reaction conditions. Remarkably, in addition to N-protected lactams, unprotected ones could also be readily reduced in the presence of a catalytic amount of weak base or even under neutral reaction conditions, which further highlights the broad substrate scope and the protocol efficiency.

Amido Complexes of Iridium with a PNP Pincer Ligand: Reactivity toward Alkynes and Hydroamination Catalysis

The pincer ligand HN(CH2CH2PPh2)2 (1; PNHP) reacted with [{Ir(μ-X)(cod)}2] (X = Cl, OMe), affording complexes [fac-(PNHP)Ir(cod)]Cl (2) and [fac-(PNP)Ir(cod)] (3), respectively. The X-ray molecular structure of 2 showed that the PNP ligand coordinates in a facial fashion, with the N atom in an axial site and both P atoms coordinated in the equatorial plane. Compound 1 is able to protonate the hydroxo bridges in the complex [{Ir(μ-OH)(coe)2}2] forming the new amido complex [mer-(PNP)Ir(coe)] (4). Complex 4 is an extremely air sensitive compound, as confirmed by the isolation of the oxo complex [mer-(PNP)Ir(σ2-O2)] (8) from its interaction with air. Protonation of 4 with HBF4 afforded the corresponding amino complex [mer-(PNHP)Ir(coe)]BF4 (5), whose molecular structure enlightened by X-ray crystallography confirmed the PNP ligand to be coordinated in a meridional fashion. The coe ligand in 4 is tightly bonded to iridium; however, under an atmosphere of ethylene at 60 °C or with acrylonitrile at 70 °C complex 4 exchanges the olefin, affording compounds [mer-(PNP)Ir(σ2-C2H4)] (6) and [mer-(PNP)Ir(σ2-C2H3CN)] (7), respectively. Interaction of 4 with alkynes depends on the nature of the substrate; therefore, methyl phenylpropiolate reacted with 4, affording the adduct [mer-(PNP)Ir(σ2-PhCCC(O)OMe)] (9), while the parent acetylene undergoes a double C-H activation, affording the Ir(III) complex [fac-(PNHP)IrH(Ca‰?CH)2] (10). A DFT theoretical analysis of this transformation supports a metal-ligand cooperation mechanism. The reaction starts by deprotonation of an alkyne moiety by the PNP ligand followed by oxidative addition of the C-H bond to the metal of a second alkyne molecule. Additionally, we have tested complex 4 as a catalyst for the addition of gaseous ammonia to activated unsaturated substrates. A DFT theoretical analysis disclosed the operative mechanism on these organic transformations, which starts with a nucleophilic attack of ammonia to the bound alkyne, hydrogen migration to the metal, and reductive elimination steps.

Iron-Catalyzed Alkylation of Nitriles with Alcohols

A general, efficient iron-catalyzed α-alkylation of nitriles with primary alcohols through a hydrogen-borrowing pathway has been developed, allowing a wide variety of alkylated nitriles to be readily accessible. Detailed mechanistic studies suggest that the reaction proceeds via an olefin intermediate with the turnover rate limited by the hydrogenation of the olefin with an iron hydride. Apart from participating in the alkylation, the nitrile is found to play an important role in promoting the formation of and stabilizing the active catalytic species.

RUTHENIUM COMPLEX, METHOD FOR PRODUCING SAME, AND USE OF SAME

The present invention provides a novel ruthenium complex that is easy to produce and handle and that can be supplied relatively inexpensively, a method for producing this ruthenium complex, a method for producing alcohols and the like using this ruthenium complex as a catalyst, a method for producing carbonyl compounds using this ruthenium complex as a catalyst, and a method for producing N-alkylamine compounds using this ruthenium complex as a catalyst. The present invention pertains to a ruthenium complex represented by general formula (1) RuX1X2(PNP) (NHC)m(Solv)n(1) (in general formula (1), X1 and X2 each independently represent a monovalent anionic monodentate ligand; PNP represents a tridentate aminodiphosphine ligand, NHC represents an N-heterocyclic carbene derived from a nitrogen-containing heterocyclic ring, and Solv represents a coordinating solvent; and m represents an integer from 1 to 3, n represents an integer from 0 to 2, and 1≦m+n≦3.), a method for producing the same, a catalyst including the same, and methods for producing various organic compounds using this catalyst.

Synthesis, characterization and catalytic application of some novel PNP-Ni(II) complexes: Regio-selective [2+2+2] cycloaddition reaction of alkyne

Some novel Ni(II) complexes of PN(H)PPh, PN(Me)PiPr and PN(Me)PtBu ligands have been synthesized and characterized using standard analytical and spectroscopic methods such as 1H NMR, 31P NMR, elemental analysis, ESI-MS, UV-Visible spectroscopy and single-crystal X-ray crystallography. In the presence of silver triflate, complex [PN(H)PPhNiBr]2NiBr4 (5) activated the C?Cl bond of dichloromethane at room temperature and afford complex [PN(H)PPhNiCl]OTf (6). We have also performed alkyne [2+2+2] cycloaddition reaction using Ni(II) complexes and observed high regioselectivity of the products. The observed selectivity is well correlating with the electronic feature of alkynes. The [2+2+2] cycloaddition of electron rich alkynes produced 1,3,5-substituted benzene derivatives as a major product whereas the electron deficient alkynes produced 1,2,4-substituted benzene derivatives as a major product.

Understanding the mechanisms of cobalt-catalyzed hydrogenation and dehydrogenation reactions

Cobalt(II) alkyl complexes of aliphatic PNP pincer ligands have been synthesized and characterized. The cationic cobalt(II) alkyl complex [(PNHP Cy)Co(CH2SiMe3)]BArF4 (4) (PNHPCy = bis[(2-dicyclohexylphosphino)ethyl]amine) is an active precatalyst for the hydrogenation of olefins and ketones and the acceptorless dehydrogenation of alcohols. To elucidate the possible involvement of the N-H group on the pincer ligand in the catalysis via a metal-ligand cooperative interaction, the reactivities of 4 and [(PNMePCy)Co(CH 2SiMe3)]BArF4 (7) were compared. Complex 7 was found to be an active precatalyst for the hydrogenation of olefins. In contrast, no catalytic activity was observed using 7 as a precatalyst for the hydrogenation of acetophenone under mild conditions. For the acceptorless dehydrogenation of 1-phenylethanol, complex 7 displayed similar activity to complex 4, affording acetophenone in high yield. When the acceptorless dehydrogenation of 1-phenylethanol with precatalyst 4 was monitored by NMR spectroscopy, the formation of the cobalt(III) acetylphenyl hydride complex [(PNHPCy)CoIII(κ2-O,C-C 6H4C(O)CH3)(H)]BArF4 (13) was detected. Isolated complex 13 was found to be an effective catalyst for the acceptorless dehydrogenation of alcohols, implicating 13 as a catalyst resting state during the alcohol dehydrogenation reaction. Complex 13 catalyzed the hydrogenation of styrene but showed no catalytic activity for the room temperature hydrogenation of acetophenone. These results support the involvement of metal-ligand cooperativity in the room temperature hydrogenation of ketones but not the hydrogenation of olefins or the acceptorless dehydrogenation of alcohols. Mechanisms consistent with these observations are presented for the cobalt-catalyzed hydrogenation of olefins and ketones and the acceptorless dehydrogenation of alcohols.

Stereospecific polymerization of 1,3-butadiene catalyzed by cobalt complexes bearing N-containing diphosphine PNP ligands

A series of cobalt complexes bearing N-containing diphosphine PNP ligands has been synthesized and characterized. The nature of the ligand structure affects the binding of the ligand to the cobalt center and determines the coordination geometry of the cobalt complexes. All the complexes have been employed to catalyze the polymerization of 1,3-butadiene, in combination with methylaluminoxane (MAO) or ethylaluminum sesquichloride (EASC) as the cocatalyst. Both the nature of the ligand and the type of cocatalyst had a remarkable influence on the polymerization activity, microstructure and molecular weight of the resulting polymers. The [Co]/MAO catalytic systems resulted in relatively lower conversions of butadiene and cis-1,4 contents in the polymers than the corresponding [Co]/EASC catalytic systems. Upon activation with EASC, the polymerization behaviors of the catalytic systems were also affected by the reaction parameters.

NOVEL RUTHENIUM CARBONYL COMPLEX HAVING TRIDENTATE LIGAND, ITS PRODUCTION METHOD AND USE

The present invention relates to a ruthenium carbonyl complex that is represented by the following Formula (1): [in-line-formulae]RuXY(CO)(L)??(1)[/in-line-formulae](in the Formula (1), X and Y, which may be the same or different from each other, represent an anionic ligand and L represents a tridentate aminodiphosphine ligand which has two phosphino groups and a —NH— group), its production method, and a method for production of alcohols by hydrogenation-reduction of ketones, esters, and lactones using the complex as a catalyst. The ruthenium carbonyl complex of the invention has a high catalytic activity and it can be easily prepared and handled.