16605-03-1Relevant articles and documents
Dinuclear Phosphine-Amido [Rh2(diene){μ-NH(CH2)3PPh2}2] Complexes as Efficient Catalyst Precursors for Phenylacetylene Polymerization
Angoy, Marta,Jiménez, M. Victoria,García-Ordu?a, Pilar,Oro, Luis A.,Vispe, Eugenio,Pérez-Torrente, Jesús J.
, p. 1991 - 2006 (2019)
Dinuclear phosphine-amido, [Rh2(diene){μ-NH(CH2)3PPh2}2], and cationic phosphine-amino complexes, [Rh(diene){Ph2P(CH2)3NHR}]+ (diene = cod, nbd, tfb) and [Rh{Ph2P(CH2)3NHR}2]+, have been prepared from the corresponding amino-functionalized phosphines Ph2P(CH2)3NHR (R = H, Me) and suitable rhodium(I) precursors. The dinuclear [Rh2(diene){μ-NH(CH2)3PPh2}2] complexes bearing π-acceptors diene ligands such as nbd or tfb exhibit a remarkable catalytic activity in phenylacetylene (PA) polymerization affording stereoregular polyphenylacetylenes with, unlike the cod precursor, unimodal molar mass distributions of very high molecular weights, Mw up to ≈ 1.2 × 106, and moderate polydispersity indexes. These complexes are more active than the mononuclear phosphino-anilido [Rh(diene){Ph2P(C6H4)NMe}] complexes, which are in turn more active than the cationic complexes [Rh(diene){Ph2P(CH2)3NHMe}]+, [Rh(nbd){Ph2P(CH2)3NH2}]+, and [Rh(nbd){Ph2P(C6H4)NHMe}]+ bearing the same diene ligand. In contrast, complexes [Rh{Ph2P(CH2)3NHR}2]+ (R = H, Me) without a diene ligand have been found to be inactive in PA polymerization. The excellent catalytic performance of [Rh2(diene){μ-NH(CH2)3PPh2}2] (diene = nbd, tfb) complexes is a consequence of the mode of activation of PA that likely results in the formation of unsaturated alkynyl species [Rh(diene)(CC-Ph)L] (L = PA, THF), which may be competent for PA polymerization.
Cobalt Phosphino-α-Iminopyridine-Catalyzed Hydrofunctionalization of Alkenes: Catalyst Development and Mechanistic Analysis
Chu, Wan-Yi,Gilbert-Wilson, Ryan,Rauchfuss, Thomas B.,Van Gastel, Maurice,Neese, Frank
supporting information, p. 2900 - 2914 (2016/11/02)
A family of CoCl2(PNpy) complexes were prepared, where PNpy = 2-iminopyridyl-phosphine ligands derived from aminoalkyl and aminoaryl phosphines and 2-keto- and 2-formylpyridines. Reduction of CoCl2(PNpy) complexes in the presence of
Phosphorus-based functional groups as hydrogen bonding templates for rotaxane formation
Ahmed, Rehan,Altieri, Andrea,DSouza, Daniel M.,Leigh, David A.,Mullen, Kathleen M.,Papmeyer, Marcus,Slawin, Alexandra M. Z.,Wong, Jenny K. Y.,Woollins, J. Derek
supporting information; experimental part, p. 12304 - 12310 (2011/10/01)
We report on the use of the hydrogen bond acceptor properties of some phosphorus-containing functional groups for the assembly of a series of [2]rotaxanes. Phosphinamides, and the homologous thio- and selenophosphinamides, act as hydrogen bond acceptors t
Aminophosphine ligands R2P(CH2)nNH 2 and ruthenium hydrogenation catalysts RuCl2(R 2P(CH2)nNH2)2
Jia, Wenli,Chen, Xuanhua,Guo, Rongwei,Sui-Seng, Christine,Amoroso, Dino,Lough, Alan J.,Abdur-Rashid, Kamaluddin
experimental part, p. 8301 - 8307 (2010/03/04)
The aminophosphine ligands R2P(CH2) 2NH2 and R2P(CH2)3NH 2 (R = Ph, iPr, tBu) were isolated in good to excellent yields from the reaction of LiPR2 with Cl(CH 2)2N(TMS)2 and Cl(CH2) 3N(TMS)2, respectively, followed by hydrolysis. This approach allows fine tuning of the ligands' stereoelectronic properties through the variation of the substituents on the phosphine. The aminophosphine ligands were used to prepare the ruthenium complexes RuCl2(R 2P(CH2)2NH2)2 and RuCl2(R2P(CH2)3NH2) 2 by reacting a 2:1 mixture of the respective ligand and [RuCl 2(cod)]n in an appropriate solvent. The resulting complexes were found to be excellent catalysts for the hydrogenation of ketones and imines. The Royal Society of Chemistry 2009.
Preparation of a Nafion-Teflon bimembrane-supported palladium catalyst and its use in the Heck reaction
Li, Yangzhou,Li, Zhiming,Li, Feng,Wang, Quanrui,Tao, Fenggang
, p. 6159 - 6162 (2007/10/03)
A novel palladium catalyst supported on the Nafion membrane, reinforced with poly(tetrafluoroethylene) fiber, has been prepared. The catalyst exhibits high activity and stability in the Heck arylation reactions of aryl iodides with olefins and Sonogashira couplings with phenylacetylene, and can be readily recovered and reused twenty times without significant loss of activity.
Polymer bound Pd(0) phosphine catalyst for homogeneous catalysis
Koshti, Nirmal,Naik, Shubhangi,Parab, Bharat
, p. 852 - 856 (2007/10/03)
Facile synthesis of water-soluble polymer bound Pd(0) phosphine catalyst is described. This recyclable polymeric catalyst is soluble in aqueous or aqueous/organic media and has high activity in nucleophilic allylic substitution, Heck reaction and hydrogenation.
Control of aminophosphine chelate ring-opening in Pt(II) and Pd(II) complexes: Potential dual-mode anticancer agents
Habtemanam, Abraha,Watchman, Beth,Potter, Brian S.,Palmer, Rex,Parsons, Simon,Parkin, Andrew,Sadler, Peter J.
, p. 1306 - 1318 (2007/10/03)
We show that bis(aminophosphine) complexes of the type [M(R1R2N(CH2)nPPh2)2 ]2+, M = Pt(II) or Pd(II), can exist in chelate ring-closed and ring-opened forms both in the solid state and in aqueous solution. The equilibrium between them in solution can be controlled by the nature of the groups R1 and R2 (H, Me, Bz, cyclohexyl), by the bridge length n, and by the pH and Cl- concentration. X-Ray crystal structures are reported for the ring-closed complexes cis-[Pt(H2N(CH2)2PPh2-P,N)2 ]Cl2, cis-[Pt(H2N(CH2)3PPh2-P,N)2 ]Cl2, and cis-[Pt(Me(H)N(CH2)2PPh2-P,N)2][HCl 2]2, the mono-ring-opened complex cis-[Pd(Me2N(CH2)2PPh2-N,P)Cl(Me 2NH(CH2)2PPh2-P)](NO3) 2, the di-ring-opened complex cis-[Pt(Me2N(CH2)3PPh2-P)2 CL2], and, for comparison, the monochelate cis-[Pd(Me2N(CH2)3PPh2-N,P)CL2 ]. These square-planar complexes exhibit varying degrees of distortion and variable M-N bond lengths dependent not only on the trans influence of P but also on steric effects within the complex, pH-induced chelate ring-opening of cis-[Pt(Me2N(CH2)2PPh2-P,N)2 ]CL2 had an associated pK value of 6.9. In contrast, complexes with R1 and R2 = H, n = 2 or 3 or R1 = H and R2 = Me, n = 2, are more difficult to ring-open. Thus the complexes cis-[Pt(Me(H)N(CH2)2-PPh2-P,N)2]CL 2 and cis-[Pt(H2N(CH2)3PPh2-P,N)2 ]CL2, had associated pK values of 2.1 and 2.9, respectively. These aminophosphine complexes may exhibit anticancer activity by two mechanisms: by disrupting mitochondrial membrane potentials as bis-chelated (ring-closed) lipophilic cations, or by direct binding to DNA bases as ring-opened complexes.
Synthesis and investigation of phosphine ligands containing cationic guanidino functions in aqueous Heck reactions
Dibowski, Harald,Schmidtchen, Franz P.
, p. 2325 - 2330 (2007/10/02)
Phosphines 2 and 3 supplemented with strongly basic and hydrophilic guanidium functions were prepared for the first time. In combination with palladium acetate these ligands form active catalysts that promote an aqueous Heck reaction.
