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Photochemistry of the luminescent alkyl complexes alkyl(carbonyl)bis(triarylphosphine)(maleonitrile-dithiolato)iridium, IrR(CO)(PAr3)2(mnt)
A series of luminescent alkyl complexes of formula IrR(CO)L2(mnt), where mnt = maleonitriledithiolate, R = Me, Et, Pr, and CH2CN, and L is a triarylphosphine, have been synthesized and characterized. The complexes posses octahedral coordination geometries with the phosphine ligands in mutually trans positions, as confirmed by a crystal structure determination of the methyl derivative. Crystal data for IrMe(CO)(PPh3)2(mnt): IrS2P2ON2C42H33, triclinic space group P1, a = 13.178(4) A, b = 13.670(4) A, c = 12.592(2) A, a = 105.03(2), beta = 115.42(2), gamma = 95.72(2), V = 1919.9 A3; Z = 2, 6298 reflections (h, ¡Àk, ¡Àl, 4 < 26 < 45), R1 = 0.020, R2 = 0.028, and GOF = 1.09. The Ir-S distances of 2.442(1) and 2.371(1) A reflect the structural influence of the trans ligands (Me and CO, respectively). The alkyl complexes luminesce in fluid solution with an emission energy in the range of 695-780 nm and a band shape that suggests vibronic structure characteristic of other mnt complexes. Photolysis of IrMe-(CO) (PPh3)2(mnt) in the presence of H-atom sources and radical traps leads to products consistent with Ir-alkyl bond homolysis. Further photochemical studies in the presence of 13CO suggest that Ir-Me bond homolysis is favored strongly over CO photodissociation. Photochemistry of IrR(CO)(PPh3)2(mnt), where R contains beta-hydrogens, produces only the beta-elimination products of olefin and the hydride complex IrH(CO)(PPh3)2(mnt) even in the presence of large excesses of phosphine, CO, or different radical trapping agents. The quantum yield for photochemical beta-elimination of 0.30 is much greater than that determined for photochemical disappearance of IrMe(CO)L2(mnt) and is consistent with an efficient H-atom transfer from R to Ir(CO)L2(mnt) within the radical pair generated by photolysis. I hope this article can help some friends in scientific research. I am very proud of our efforts over the past few months and hope to 1038-95-5, help many people in the next few years., Application of 1038-95-5
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Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate