Ruthenium piano-stool complexes bearing imidazole-based PN ligands

Abstract

A variety of piano-stool complexes of cyclopentadienyl ruthenium(II) with imidazole-based PN ligands have been synthesized starting from the precursor complexes CpRu(C10H8)]PF6, CpRu(NCMe)(3)]PF6 and CpRu(PPh3)(2)Cl]. PN ligands used are imidazol-2-yl, -4-yl and -5-yl phosphines. Depending on the ligand and precursor different types of coordination modes were observed; in the case of polyimidazolyl PN ligands these were kappa P-1-monodentate, kappa P-2,N-, kappa N-2,N-and kappa N-3,N,N-chelating and mu-kappa P:kappa N-2,N-brigding. The solid-state structures of CpRu(1a)(2)Cl]center dot H2O (5 center dot H2O) and CpRu(mu-kappa(2)-N,N-kappa('1)-P-2b)(2)](C6H5PO3H)(2)(C6H5PO3H2)( 2), a hydrolysis product of the as well determined CpRu(2b) (2)](PF6)(2)center dot 2CH(3)CN (7b center dot 2CH(3)CN) were determined (1a = imidazol-2-yldiphenyl phosphine, 2b = bis(1-methylimidazol-2-yl) phenyl phosphine, 3a = tris(imidazol-2-yl) phosphine). Furthermore, the complexes CpRu(L) (2) [e] Anorganisch-Chemisches Institut, Universität Zürich-Irchel, Winterthurerstr. 190, CH-8057 Zürich, Switzerland.[ ‡] X-ray structure analysis.

New iminophosphine–Ru(II) complexes and their application in hydrogenation and transfer hydrogenation

“…The synthesis of many important drugs is accomplished by reducing ketones, aldehydes and imines via hydrogenation and transfer hydrogenation processes. Especially after Noyori's studies on hydrogenation with phosphine ligands, researchers have continuously derived phosphine ligands and analysed their efficiency in the hydrogenation and transfer hydrogenation of metal complexes . It is known that the catalytic efficiency of hemilabile phosphine derivative PN ligands increases in the catalytic reactions of Ru(II) complexes.…”

Revisiting tubercidin against kinetoplastid parasites: Aromatic substitutions at position 7 improve activity and reduce toxicity

“…13 C NMR (75 MHz, DMSO-d6) δ: 31.5 (CH3), 61.6 (C-5'), 70.5 (C-3'), 73.9 (C-2'), 85.1 (C-4'), 87.4 (C-1'), 101.7 (C-4a), 102.3 (C-5), 123.0 (C-6), 125.1 (C-5Imid), 128.3 (C-4Imid), 139.4 (C-2Imid), 150.3 (C-7a), 152.0 (C-2), 157.3 (C-4). HRMS (ESI): calculated for C15H19N6O4 ([M+H] + ): 347.1462, found: 347.1481.4-amino-5-(1-methyl-1H-imidazol-4-yl)-N7-(β-D-ribofuranosyl)-pyrrolo[2,3-d]pyrimidine (20) 20was prepared according to General Procedure B, employing 1-methyl-4-(tributylstannyl)-1Himidazole[38][39] as the coupling partner. The mixture was purified by column chromatography 0 → 3.5 % MeOH / DCM.…”

The synthesis and transformation of 4-phosphorylated derivatives of 1,3-azoles

“…Для отримання біс-та трис[імідазол-4(5)-іл] фосфінів в серії робіт [5][6][7][8][9][10][11][12][13][14][15][16] використано 2-заміщені імідазоли, які перед фосфорилюванням також попередньо захищають по N 1 атому. Захисними використовуються стійкі до дії основ групи: СH 2 OMe та СH(OEt) 2 , які легко знімаються 20 % соляною кислотою або водним ацетоном відповідно (схема 2).…”