Microwave‐Assisted Organometallic Syntheses: Formation of Dinuclear [(Arene)Ru(μ‐Cl)₃RuCl(L–L′)] Complexes (L–L′: Chelate Ligands with P‐, N‐, or S‐Donor Atoms) by Displacement of Arene π Ligands

Abstract

Microwave heating was employed to promote arene displacement in reactions of [{(p‐cymene)RuCl2}2] or [{(1,3,5‐C6H3iPr3)RuCl2}2] with neutral chelate ligands L–L′ [L–L′: 1,1′‐bis(diphenylphosphanyl)methane, 1,1′‐bis(diphenylphosphanyl)ferrocene, (S)‐BINAP, (S,S)‐DIOP, N,N′‐bis(2,4,6‐trimethylphenyl)‐1,2‐ethanediylidenediamine], (R)‐Ph‐PHOX, and 3‐(phenylsulfanylpropyl)diphenylphosphane. The reactions gave complexes of the general formula [(arene)Ru(μ‐Cl)3RuCl(L–L′)] in good yield. The synthesis of [(p‐cymene)Ru(μ‐Cl)3RuCl{PPh2(CH2)3NH2}] (22) was accomplished in two steps via the intermediate [{(p‐cymene)RuCl2}2{μ‐PPh2(CH2)3NH2}] (21). The structures of [(1,3,5‐C6H3iPr3)Ru(μ‐Cl)3RuCl(dppf)] (16), [(1,3,5‐C6H3iPr3)Ru(μ‐Cl)3RuCl{(S)‐BINAP}] (17), and [(p‐cymene)Ru(μ‐Cl)3RuCl(MesNCHCHNMes)] (18) were determined by single‐crystal X‐ray diffraction.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

1,2,3-Triazolylidene ruthenium(ii)(η6-arene) complexes: synthesis, metallation and reactivity

“…The displacement of coordinated p-cymene moiety is well precedented in the literature. [40][41][42][43][44][45][46][47] Certainly p-cymene fragments has been displaced by phosphines, bis-phosphines or donor solvent such as acetonitrile but in addition, intramolecular displacement of p-cymene moiety by the pendant arene rings attached to the already coordinated ligands has also been previously observed.…”

Schiff Bases as Inspirational Motif for the Production of Ni(II) and Pd(II) Coordination and Novel Non‐Symmetric Ni(II)‐POCOP Pincer Complexes

“…In this context, the Suzuki‐Miyaura reaction is amongst the best‐studied metal‐catalysed coupling process due to its relevance for the synthesis of active pharmaceutical ingredients, materials and others industrial relevant intermediates [27a,28] . Likewise, the applications of these metal systems and the use of alternative energy sources, such as microwave irradiation (MW) to generate more eco‐friendly, economical and sustainable protocols are themes of great relevance nowadays [29] . The use of microwave irradiation has undeniable advantages compared to conventional heating affording shorter reaction times, faster reaction kinetics and cleaner products.…”

“…[27a,28] Likewise, the applications of these metal systems and the use of alternative energy sources, such as microwave irradiation (MW) to generate more eco-friendly, economical and sustainable protocols are themes of great relevance nowadays. [29] The use of microwave irradiation has undeniable advantages compared to conventional heating affording shorter reaction times, faster reaction kinetics and cleaner products. Thus, we evaluated the catalytic activity of the series of newly synthesized coordination and organometallic complexes in Suzuki-Miyaura couplings using microwave irradiation in a model reaction between bromobenzene and phenylboronic acid under optimized reaction conditions previously established in our laboratory [21] for analogous catalytic systems (Na 2 CO 3 , DMF/H 2 0, 4 : 1 (5 mL), 150 W, 20 min) as summarized in Table 3 (Entries 1-6).…”

Metal–Arene Complexes with Indolo[3,2-c]-quinolines: Effects of Ruthenium vs Osmium and Modifications of the Lactam Unit on Intermolecular Interactions, Anticancer Activity, Cell Cycle, and Cellular Accumulation

“…All complexes have a typical “three-leg piano-stool” geometry of ruthenium(II) and osmium(II) arene complexes, 53−56 with an η 6 -π-bound p -cymene ring forming the seat and three other donor atoms (two nitrogens N12 and N15 of indolo[3,2- c ]quinoline and one chlorido ligand) as the legs of the stool. Selected bond distances and angles are given in Table 1.…”