14871-41-1Relevant articles and documents
Reactions of nitrilium triflate salts with trans-
Barber, Michael,Booth, Brian L.,Bowers, Philip J.,Tetler, Lee
, p. C25 - C28 (1987)
Low yields of the ionic carbene complexes O3SCF3 (R=Ph or PhCH2) have been isolated from the reactions of trans- with the nitrilium triflate salts, NMe>O3SCF3.The major products from these, and the
Barber, Michael,Booth, Brian L.,Bowers, Philip J.,Tetler, Lee
, p. C25 - C28 (1987)
Low yields of the ionic carbene complexes O3SCF3 (R=Ph or PhCH2) have been isolated from the reactions of trans- with the nitrilium triflate salts, NMe>O3SCF3.The major products from these, and the
Unusual behavior in the 308 nm flash photolysis of Vaska's complex
Schultz, Richard H.
, p. 1 - 4 (2003)
Time-resolved IR absorption spectroscopy was used to investigate the photolysis of Vaska's Complex (VC), trans-(PPh3)2 Ir(CO)(Cl). Upon 308 nm photolysis, an intermediate was formed that regenerated VC on a millisecond timescale. This intermediate was not formed at the laser flash, but was generated over the course of ～10 μs. Most unusually, there was no evidence for prompt bleach of the C-O stretch of VC upon photolysis. Evidence was presented that the intermediate from which regeneration of VC occurred was a dimeric species. Possible pathways for the generation of the dimeric intermediate are discussed.
Systematic Study of the Stereoelectronic Properties of Trifluoromethylated Triarylphosphines and the Correlation of their Behaviour as Ligands in the Rh-Catalysed Hydroformylation
Herrera, Daniel,Peral, Daniel,Cordón, Mercedes,Bayón, J. Carles
supporting information, p. 354 - 363 (2020/12/30)
The stereoelectronic properties of a series of trifluoromethylated aromatic phosphines have been studied using different approaches. The σ-donating capability has been evaluated by nuclear magnetic resonance (NMR) spectroscopy of the selenide derivatives and the protonated form of the different trifluoromethylated phosphines. The coupling constants between phosphorous and selenium (1JSeP) and phosphorous and hydrogen (1JHP) can be predicted by empirical equations and correlate the basicity of the phosphines with the number and relative position of trifluoromethyl groups. In contrast, the π-acceptor character of the ligands has been evaluated by measuring the frequency of the CO vibration in the infrared (IR) spectra of the corresponding Vaska type iridium complexes ([IrCl(CO)(PAr3)2], PAr3=triarylphosphine). Moreover, the correlation between the electronic properties and the performance of these phosphines as ligands in the rhodium-catalysed hydroformylation of 1-octene has been established. Phosphines with the lowest basicity, that are those with the highest number of trifluoromethyl groups, gave rise to more active catalytic systems.
ENAMINE COMPOUND AND USE THEREOF
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Paragraph 0111; 0115-0120, (2020/03/28)
Provided are a donor-acceptor type compound having a novel structure and its use. An enamine compound represented by general formula (1) (in the formula: R1 represents an electron-withdrawing group;A represents a divalent aromatic hydrocarbon group which may contain a substituent, a divalent aromatic heterocyclic group which may contain a substituent or a divalent unsaturated aliphatic hydrocarbon group which may contain a substituent;R2 represents a hydrogen atom or a hydrocarbon group which may contain a substituent;R3 and R4 are the same or different from each other and represent an aromatic hydrocarbon group which may contain a substituent or an aromatic heterocyclic group which may contain a substituent, or R3 and R4 together form an optionally substituted bicyclic aromatic heterocyclic group containing two or more nitrogen atoms or a nitrogen atom and an oxygen atom or a sulfur atom, or a tricyclic aromatic heterocyclic group which may contain a substituent; andR2 and A, or R2 and R3 may together form a cyclic structure).
Experimental and theoretical mechanistic investigation of the iridium-catalyzed dehydrogenative decarbonylation of primary alcohols
Olsen, Esben P. K.,Singh, Thishana,Harris, Pernille,Andersson, Pher G.,Madsen, Robert
supporting information, p. 834 - 842 (2015/01/30)
The mechanism for the iridium-BINAP catalyzed dehydrogenative decarbonylation of primary alcohols with the liberation of molecular hydrogen and carbon monoxide was studied experimentally and computationally. The reaction takes place by tandem catalysis through two catalytic cycles involving dehydrogenation of the alcohol and decarbonylation of the resulting aldehyde. The square planar complex IrCl(CO)(rac-BINAP) was isolated from the reaction between [Ir(cod)Cl]2, rac-BINAP, and benzyl alcohol. The complex was catalytically active and applied in the study of the individual steps in the catalytic cycles. One carbon monoxide ligand was shown to remain coordinated to iridium throughout the reaction, and release of carbon monoxide was suggested to occur from a dicarbonyl complex. IrH2Cl(CO)(rac-BINAP) was also synthesized and detected in the dehydrogenation of benzyl alcohol. In the same experiment, IrHCl2(CO)(rac-BINAP) was detected from the release of HCl in the dehydrogenation and subsequent reaction with IrCl(CO)(rac-BINAP). This indicated a substitution of chloride with the alcohol to form a square planar iridium alkoxo complex that could undergo a β-hydride elimination. A KIE of 1.0 was determined for the decarbonylation and 1.42 for the overall reaction. Electron rich benzyl alcohols were converted faster than electron poor alcohols, but no electronic effect was found when comparing aldehydes of different electronic character. The lack of electronic and kinetic isotope effects implies a rate-determining phosphine dissociation for the decarbonylation of aldehydes.
Phosphine, isocyanide, and alkyne reactivity at pentanuclear molybdenum/tungsten-iridium clusters
Simpson, Peter V.,Randles, Michael D.,Gupta, Vivek,Fu, Junhong,Moxey, Graeme J.,Schwich, Torsten,Morshedi, Mahbod,Cifuentes, Marie P.,Humphrey, Mark G.
supporting information, p. 7292 - 7304 (2015/04/27)
The trigonal bipyramidal clusters M2Ir3(μ-CO)3(CO)6(η5-C5H5)2(η5-C5Me4R) (M = Mo, R = Me 1a, R = H; M = W, R = Me, H) reacted with iso
Slow exchange of bidentate ligands between rhodium(I) complexes: Evidence of both neutral and anionic ligand exchange
Chen, Si,Manoury, Eric,Poli, Rinaldo
, p. 5820 - 5826 (2015/02/19)
The phosphine double exchange process involving [RhCl(COD)(TPP)] and [Rh(acac)(CO)(TMOPP)] (TPP = PPh3, TMOPP = P(C6H4-4-OMe)3) to yield [RhCl(COD)(TMOPP)] and [Rh(acac)(CO)(TPP)] is very rapid but is followed by a much slower process where the bidentate ligands are exchanged to yield [Rh(acac)(COD)] and a mixture of [RhCl(CO)(TPP)2], [RhCl(CO)(TMOPP)2], and [RhCl(CO)(TPP)(TMOPP)]. The exchange involving [RhCl(COD)(L)] and [Rh(acac)(CO)(L)] yields [Rh(acac)(COD)] and [RhCl(CO)(L)2], where the reaction is much faster when L = TPP than when L = TMOPP. The mixed-metal system comprising [IrCl(COD)(TPP)] and [Rh(acac)(CO)(TPP)] yields all four complexes [M(acac)(COD)] and [MCl(CO)(TPP)2], where M = Rh and Ir. This illustrates that both a neutral ligand exchange and an anionic ligand exchange occur. Possible pathways for these processes are discussed.
Facile N-N activation in benzotriazole: Capturing the dimroth azo/triazole intermediate by complexation to iridium
Bohle, D. Scott,Chua, Zhijie,Perepichka, Inna
, p. 1304 - 1310 (2013/11/06)
The in situ observation of benzotriazole ring and ring-opened isomers, which result from the Dimroth equilibrium for 1-[(nonafluorobutane) sulfonyl]benzotriazole, 1, in solution by 19F NMR and UV/Vis spectroscopy is reported. Two benzotriazoles
Comparative reactivity of triorganosilanes, HSi(OEt)3 and HSiEt3, with IrCl(CO)(PPh3)2. Formation of IrCl(H)2(CO)(PPh3)2 or Ir(H)2(SiEt3)(CO)(PPh3
Nishihara, Yasushi,Takemura, Miwa,Osakada, Kohtaro
, p. 2951 - 2956 (2009/10/01)
Reaction of HSi(OEt)3 with IrCl(CO)(PPh3)2 (5:1 molar ratio) at room temperature for 1 h gives IrCl(H){Si(OEt)3}(CO)(PPh3)2 (1), which is observed by the 1H and 31P{s
Unexpected formation of a weak metal-metal bond: Synthesis, electronic properties, and second-order NLO responses of push-pull late-early heteronuclear bimetallic complexes with W(CO)3(1,10-phenanthroline) acting as a donor ligand
Pizzotti, Maddalena,Ugo, Renato,Dragonetti, Claudia,Annoni, Elisabetta,Demartin,Mussini
, p. 4001 - 4011 (2008/10/08)
In attempts to bridge the complex [W(CO)3(phen)(pyz)] (phen = 1,10-phenanthroline; pyz = pyrazine) to acceptor centers, either soft centers such as cis-M(CO)2CL (M = Rh(I), Ir(I)) and fac-M(CO)3Cl2 (M = Ru(II), Os(II)) or hard centers such as BF3, the pyrazine ligand is lost, while the fragment W(CO)3(phen) behaves as a σ-donor base with the unexpected formation of heteronuclear early-late bimetallic compounds with a weak metal-metal bond, as confirmed by the easy substitution of W(CO)3(phen) by soft ligands (PPh3, CO, pyridine). The X-ray structures of [(CO)3(phen)W-cis-Ir(CO)2Cl] and [(CO)3(phen)W-fac-Os(CO)3Cl2] confirm a single metal-metal bond with an halogen bridging asymmetrically the two metallic moieties and with the tungsten atom achieving a distorted (6 + 1) octahedral coordination. All the heteronuclear bimetallic complexes investigated show in their electronic spectra a new solvatochromic absorption band at around 385-450 nm in addition to the MLCT (W→π*phen) absorption band typical of [W(CO)3(phen)L] complexes (L = CO, pyz, CH3CN) and an increased, in comparison to [W(CO)4(phen)], negative nonlinear (NLO) second-order emission working with the EFISH technique with an incident wavelength of 1.907 μm. The increase is due to an additional negative contribution of the new absorption band at around 385-450 nm, as shown by a solvatochromic investigation.
