54005-98-0Relevant academic research and scientific papers
Selective ethylene oligomerization with in-situ-generated chromium catalysts supported by trifluoromethyl-containing ligands
Choi, Eung Man,Park, Jong-Eun,Park, Gyeong Su,Shong, Bonggeun,Kang, Sung Kwon,Son, Kyung-Sun
, p. 444 - 450 (2018)
A series of pyrrole-containing diarylphosphine and diarylphosphine oxide ligands were prepared. The catalytic activity of the corresponding in-situ-generated chromium catalysts was investigated during selective ethylene oligomerization reactions. Variatio
LIGAND COMPOUND, ORGANIC CHROMIUM COMPOUND, CATALYST SYSTEM FOR OLIGOMERIZATION OF OLEFINS AND METHOD FOR OLIGOMERIZATION OF OLEFINS USING THE CATALYST SYSTEM
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Paragraph 0108; 0115-0117, (2017/06/20)
The present invention relates to a ligand compound, a catalyst system for olefin oligomerization, and an oligomerization method of olefin using the same. The ligand compound according to the present invention can be applied to the catalyst system for olefin oligomerization, thereby being able to exhibit improved 1-hexene selectivity and catalytic activity.COPYRIGHT KIPO 2017
Broad HOMO-LUMO gap tuning through the coordination of a single phosphine, aminophosphine or phosphite onto a Ru(tpy)(bpy)2+ core
Dixon, Isabelle M.,Lebon, Emilie,Loustau, Gilles,Sutra, Pierre,Vendier, Laure,Igau, Alain,Juris, Alberto
body text, p. 5627 - 5635 (2009/02/07)
The synthesis of new ruthenium(ii) terpyridine bipyridine complexes bearing a phosphorus(iii) ligand is presented. The steric and electronic properties of the phosphorus ligand were varied using aminophosphines, alkyl and aryl phosphites and the bulky tri(isopropyl)phosphine. All complexes were characterized by multi-nuclear NMR spectroscopy, mass spectrometry and X-ray diffraction analysis. The electronic properties of the complexes were probed by cyclic voltammetry, absorption and luminescence spectroscopy. The complexes do not show luminescence at room temperature, whereas at 77 K in an alcoholic matrix, emission is observed in the range 600-650 nm with lifetimes of 3.5-5.5 μs, originating from 3MLCT states. The MLCT transition spans over 65 nm, which corresponds to a variation of 0.4 eV in the HOMO-LUMO gap. The oxidation potential of the ruthenium varies over a broad range of 290 mV, from +1.32 V vs. SCE with L = PiPr3 to +1.61 V vs. SCE with L = P(OPh)3. This range is unprecedented upon the variation of a single monodentate ligand coordinated by the same heteroatom in the same oxidation and charge states. This work underlines the specific capacity of phosphorus in bringing up a large variety of electronic properties by changing its substituents.
Synthesis of pyrrolyl-, indolyl-, and carbazolylphosphanes and their catalytic application as ligands in the hydroformylation of 2-pentene
Jackstell, Ralf,Klein, Holger,Beller, Matthias,Wiese, Klaus-Diether,Roettger, Dirk
, p. 3871 - 3877 (2007/10/03)
The synthesis of π-acceptor ligands of the type PArxR3-x (x = 0-2; R = pyrrolyl, indolyl, carbazolyl; Ar = aryl) (1-8, 10, 12, 13) and P(pyrrolyl)2(carbazolyl) (11) is described. These ligands can be prepared in good to excellent yields by treatment of the corresponding free heterocyclic amines with phosphorus chlorides in the presence of base. The utilization of pyrrolyl-, indolyl-, and carbazolylphosphanes in the rhodium-catalyzed hydroformylation of 2-pentene demonstrates the influence of the ligand π-acidity on regioselectivity and activity in the hydroformylation of internal olefins. In general, increasing π-acidity of the ligand results in an increased yield of the linear oxo product. The best n/iso ratios of about 60:40 are obtained at low synthesis gas pressure (10 bar) in the presence of the P(pyrrolyl)3 (1) ligand.
Aminodiphenylphosphanes: Isotope-induced chemical shifts 1Δ14/15N(31P), coupling constants 1J(31P,15N), and chemical shifts δ15N and δ31P
Contreras, Rosalinda,Grevy, Jean Michel,Garcia-Hernandez, Zureima,Goeizado-Rodriguez, Marisol,Wrackmeyer, Bernd
, p. 542 - 550 (2007/10/03)
A series of aminodiphenylphosphanes 1 [Ph2P-N(H)tBu (a), -NEt2 (b), -NiPr2 (c)], 2 [Ph2P-NHPh (a), -NH-2-pyridine (b), -NH-3-pyridine (c), -NH-4-pyridine (d), NH-pyrimidine (e), NH-2,6-Me2-C6/su
N-pyrrolyl phosphines: An unexploited class of phosphine ligands with exceptional π-acceptor character
Moloy, Kenneth G.,Petersen, Jeffrey L.
, p. 7696 - 7710 (2007/10/02)
The coordination chemistry of N-pyrrolyl phosphines (P-NC4H4) is described. These ligands are prepared in excellent yield from pyrrole, a phosphorus halide, and base, and this synthesis has been applied to the series PPhx(pyrrolyl)3-x (x = 0-2) and the chelate (pyrrolyl)2P(CH2)2P(pyrrolyl)2. These ligands readily form coordination complexes, and the complexes trans-RhCl(CO)[PPhx(pyrrolyl)3-x]2 (x = 0-2) and Mo(CO)4[(pyrrolyl)2P(CH2) 2-P(pyrrolyl)2] are described. The carbonyl stretching frequencies of these complexes are shifted to significantly higher energy relative to "traditional" phosphine ligands, indicating that N-pyrrolyl phosphines are poor σ-donors, exceeding phosphites and approaching fluoroalkylphosphines with respect to this property. For example, νCO for trans-RhCl(CO)-[P(pyrrolyl)3]2 exceeds that of the PPh3 analogue by 59 cm-1. That these ligands are π-acceptors is suggested by the single crystal X-ray structure of trans-RhCl(CO)[P(pyrrolyl)3]2 which shows shortened Rh-P distances and a lengthened Rh-C distance, consistent with enhanced Rh to P back-bonding. The X-ray structure of trans-RhCl(CO)-[P(pyrrolidinyl)3]2 is also reported; this complex possesses longer Rh-P distances which more closely resemble those found for other complexes of this type. The exceptional π-acceptor character of these ligands is convincingly demonstrated by their substitution chemistry with electron rich [PPN][Rh(CO)4]. P(pyrrolyl)3 is found to displace CO in a stepwise manner to give the entire series [PPN][Rh(CO)4-x{P(pyrrolyl)3}xr] (x = 1-4). Similar results are obtained with (pyrrolyl)2P(CH2)2P(pyrrolyl)2, and the anions [PPN][Rh(CO)x{(pyrrolyl)2P(CH2) 2P(pyrrolyl)2}y] (x = 2, y = 1; x = 0, y = 2) are reported. An X-ray structure analysis of [PPN][Rh(CO){P(pyrrolyl)3}3] shows that the Rh-P bonds in this tetrahedral anion are shorter than those found in the Rh(I) complex, consistent with significantly greater π back-bonding in this more electron rich system. The infrared spectra of these anions again show a substantial shift in νCO to higher frequency relative to other phosphine ligands. The structural results further indicate that PPhx(pyrrolyl)3-x (x = 0-2), PPh3, and P(pyrrolidinyl)3 possess nearly identical steric properties (cone angles). The wide range of electronic properties (π-acceptor/σ-donor) exhibited by this isosteric series, together with their ready availability, suggests that they, and N-pyrrolyl phosphines in particular, may find utility in physical inorganic and organometallic chemistry.
