171198-88-2

Upstream product

• 1259-35-4 tris(pentafluorophenyl)phosphine 
• 201230-82-2 carbon monoxide 
• 14243-22-2 chlorodicarbonyl(p-toluidine)iridium 

Relevant academic research and scientific papers

Reactions of Singlet Oxygen with Organometallic Complexes. 3. Kinetics and Scope of the Oxidative Addition Reaction of Singlet Oxygen with Iridium(I), Rhodium(I), and Platinum(II) Complexes

Photosensitized oxidation of a series of iridium(I) complexes of the type trans-Ir(CO)X(PPh3)2 (X = halogen) leads to the same iridium(III) dioxygen complexes as the reaction with triplet oxygen. The reaction with singlet oxygen is many orders of magnitude faster than the triplet oxygenreactions. In contrast to those for the reaction with triplet oxygen, the rate constants for the (1)O2 reaction and physical deactivation do not vary significantly with different ligands, except for extremely electron-poor complexes, where there is no interaction between the complex andsinglet oxygen. The analogous rhodium(I) complexes show very similar reactivity. The resulting previously unknown rhodium(III) dioxygen complexes are unstable at room temperature. Related square-planar platinum(II) complexes do not show any interaction with singlet oxygen, except for trans-PtHCl(PEt3)2, which gives some physical deactivation of singlet oxygen; however, with this compound, no reaction product could be detected even at low temperature. The results suggest that many metal complexes may react with singlet oxygen to form novel metal-dioxygen complexes.

The electron-poor phosphines P{C6H3(CF 3)2-3,5}3 and P(C6F 5)3 do not mimic phosphites as ligands for hydroformylation. A comparison of the coordination chemistry of P{C 6H3(CF3)2-3,5}3 and P(C6F5)3

The fluoroaryl phosphines P{C6H3(CF3) 2-3,5}3 (La) and P(C6F 5)3 (Lb) form the complexes trans-[MCl 2(La)2] and trans-[MCl2(L b)2] (M = Pd or Pt) which have been isolated and fully characterised. 31P NMR studies of competition experiments show that the stability of trans-[PdCl2L2] is in the order L = Lb a 3. The crystal structure of trans-[PtCl2(La)2] is reported and reveals that the Pt-P bond lengths in trans-[PtCl2L2] are in the order L = Lb a 3. The equilibria established when [Pt(norbornene)3] is treated with La or Lb are investigated by 31P and 195Pt NMR spectroscopy and the species [PtLn(norbornene)3-n] (n = 1-3) identified. Ligands La and Lb appear to have similar affinities for platinum(0). The complexes trans-[MCl(CO)(La) 2] and trans-[MCl(CO)(Lb)2] (M = Rh or Ir) have been synthesised and fully characterised; the values of vco are comparable with those for analogous phosphite complexes. The ligands L a, Lb, P(C6H2F 3-3,4,5)3 (Lc), P{C6H 4(CF3)-2}3 (Ld), PPh3 and P(OPh)3 have been tested in rhodium-catalysed hydroformylation of 1-hexene and La, Lb, and PPh3 have been tested in rhodium-catalysed hydroformylation of 4-methoxystyrene. Ligands L a, and Lb, have been shown to be stable under the hydroformylation catalysis conditions. For the 1-hexene reaction, the activity and selectivity for La and Lc are very similar to the PPh3 catalyst (TOF ca. 400 h-1; n: iso 2.5-3.0) but for the sterically demanding Lb and Ld the activity and selectivity was much lower than with PPh3 (TOF ca. 15, n: iso ratio 0.6). Thus, the yield of heptanals obtained with the catalyst derived from La is 94% while under the same conditions with Lb only 6%. The TOF for the La/Rh catalyst was 5 times lower than for the P(OPh)3/Rh catalyst despite the superficially similar ligand electronic characteristics for La and P(OPh)3. The Royal Society of Chemistry 2005.

Tris(pentafluorophenyl)phosphine complexes of iridium: Molecular structure of trans-IrBr(CO){P(C6F5)3}2

The first tris(pentafluorophenyl)phosphine complexes of iridium, IrX (CO){P(C6F5)3}2 (X = Cl, Br), formed by the reaction between IrX3 and P(C6F5)3 in 2-methoxyethanol