252930-76-0

Downstream Products

• 561297-18-5 (η5-cyclopentadienyl)(dppe)Ru((N2)-4,5-bis(methoxycarbonyl)-1,2,3-triazolato) 
• 561297-20-9 (η5-cyclopentadienyl)(dppe)Ru((N2)-4-cyano-1,2,3-triazolato) 
• 561297-21-0 (η5-cyclopentadienyl)(dppe)Ru(N4CC(CN)C(CN)2) 

Relevant academic research and scientific papers

Syntheses, characterization and structure determination of {[CpRu(X)]2(η2,μ2-dppe)2} complexes (X=Cl, N3; Dppe=Ph2PCH2CH2PPh2): Chelating vs. bridging behavior of a classical bidentate ligand

Phosphine substitution reactions between (η5-C5H5)Ru(PPh3)2Cl (1) and 1,2-bis(diphenylphosphino)ethane (Ph2P(CH2)2PPh2, dppe), in refluxing benzene or in toluene at 80°C afforded a mixture of complexes where dppe behaves both as a bridging and as a chelating ligand. CpRu(η2-dppe)Cl (2) and {[CpRu(Cl)]2(η2,μ2-dppe)2} (3) were separated by fractional precipitation from the reaction mother-liquor, and were characterized by 1H, 13C, 31P NMR, elemental analysis and IR spectroscopy. The (2):(3) ratio in the composition of the reaction product was found to be independent of the reaction time. In solution and at room temperature, (3) exists in both boat and chair conformers of a 10-membered ring, while at lower temperatures, and in the solid-state, only the chair conformer is observed. Compounds (2) and (3) undergo halide-displacement upon reacting with NaN3 in the presence of ethanol to yield CpRu(η2-dppe)(N3) (4) and {[CpRu(N3)]2(η2,μ2-dppe) 2} (5), respectively. The crystal structures of (3) and (5) were determined. Elsevier Science Ltd.

Facile synthesis of 1,5-disubstituted 1,2,3-triazoles by the regiospecific alkylation of a ruthenium triazolato complex

The alkylation of the N(2)-bound ruthenium triazolate [Ru]N3C2HCO2Et (2, [Ru] = (η5-C5H5)(dppe)Ru, dppe = Ph2PCH2CH2PPh2) with benzylbromides is reported. The regiospecific alkylation of 2, which results from the [3 + 2] cycloaddition of ethyl propiolate with [Ru]-N3 (1), gives a series of cationic N(1)-bound N(3)-alkylated-4-ethoxycarbonyl triazolato complexes {[Ru]N3(CH2R)C2HCO2Et}[Br] (3a, R = 4-CH2Br-C6H4; 3b, R = 3,5-(CH2Br)2-C6H3; 3c, R = 2,6-F2-C6H3; 3d, R = 4-CN-C6H4) and the subsequent cleavage of the Ru-N bond of 3a-3d gives N(1)-alkylated-5-ethoxycarbonyl triazoles N3(CH2R)C2HCO2Et (4a-4d) and [Ru]-Br, which, on reacting with sodium azide, would afford [Ru]-N3 (1) thus forming a reaction cycle. The treatment of {[Ru]N3(CH2C6F5)C2HCO2Et}[Br] (3e) with sodium azide in refluxing ethanol gives the free triazole N3(CH2C6F5)C2HCO2Et (4e) and 1. The treatment of 2 with an equivalent of 3a affords a dinuclear bis(triazolato) complex {α,α′-bis([Ru]N3C2HCO2Et)-p-xylene}[Br]2 (5) and an organic bis(triazole) complex α,α′-bis(N3C2HCO2Et)-p-xylene (6). The treatment of 2 with CF3COOH in CHCl3 at room temperature affords a mixture of N(2)-bound 1H- and 3H-4-ethoxycarbonyl triazolato complexes {[Ru]N3HC2HCO2Et}[CF3COO] (1H-7) and (3H-7) in a ratio of 5?:?2. The structures of 4e, 5 and 1H-7 were confirmed by single-crystal X-ray diffraction analysis.

Synthesis, characterisation and molecular structure of Ru-Sn(II) containing derivatives

A series of new ruthenium-based derivatives were obtained by reactions of [Ru(η-C5H5)(PPh3)2Cl]. They are as follows: [Ru(η- C5H5)(PPh3)2SnF3] (1), [Ru(η-C5H5)(PPh3)2 SnCl3] (2), [Ru(η-C5H5)(PPh3)2 SnBr3] (3), [Ru(η-C5H5)(dppe)SnF3] (4), [Ru(η-C5H5)(dppe)SnCl3] (5), and [Ru(η-C5H5)(dppe)SnBr3] (6). Compounds 1-6 were studied by IR, NMR (1H, 13C, 31P and 119Sn) and 119Sn Mo?ssbauer spectroscopies. In addition, 1, 2, 3 and 6 were structurally authenticated by X-ray crystallographic studies. Finally all the derivatives were tested as catalysts in the methanol to acetic acid conversion process, showing promising activities.

Facile synthesis of 1,5-disubstituted tetrazoles by reacting a ruthenium acetylide complex with trimethylsilyl azide

Treatment of [Ru]-CCPh (1, [Ru] = (η5-C5H5)(dppe)Ru, dppe = Ph2PCH2CH2PPh2) with trimethylsilyl azide afforded the cationic nitrile complex {[Ru]NCCH2Ph}[N3

Synthesis of 1,4,5-trisubstituted triazoles by [3+2] cycloaddition of a ruthenium azido complex with ynoate esters

The [3 + 2] cycloaddition reactions of a series of ynoate esters with a ruthenium azido complex [Ru]?N3 (1, [Ru] = (η5-C5H5)(dppe)Ru, dppe = Ph2PCH2CH2PPh2) were inves

Synthesis of ruthenium triazolato and tetrazolato complexes by 1,3-dipolar cycloadditions of ruthenium azido complex with alkynes and alkenes and regiospecific alkylation of triazolates

The [3+2] cycloaddition reactions of alkynes and alkenes with ruthenium azido complex [Ru]-N3 (1, [Ru] = (η5-C5H5)(dope)Ru, dppe = Ph2PCH2CH2PPh2) have been investigated. The metal-bound heterocyclic complexes produced are triazolates [Ru]N3C2(CO2Me)2 (2) and [Ru]N3C2HCO2Me (3) from dimethyl acetylene dicarboxylate and methyl propiolate, respectively. Reaction of 1 with fumaronitrile in CH2Cl2 at room temperature results in removal of a HCN molecule and produces the triazolato complex [Ru]N3C2HCN (4). In contrast, reaction of tetracyanoethene with 1 affords the tetrazolato complex [Ru]N4C[C(CN)=C(CN)2] (5). The structures of these complexes are all clearly established as N(2)-bound. Alkylation of 2 with organic bromides causes cleavage of the Ru - N bond and affords [Ru]-Br and N(1)-alkylated five-membered-ring organic triazoles N3(R)C2(CO2Me)2 (6a, R = CH2C6F5; 6b, R = CH2Ph; 6c, R = CH2CO2Me). Reaction of 3 with excess methyl propiolate gives a mixture of Z- and E-form zwitterionic N(1)-bound N(3)-alkylated-4-substituted triazolato complexes [Ru]N3(CH=CHCO2Me)C2H(CO2) (7) in a ratio of ca. 4:1. Reaction of (Z)-7 with ICH3 affords {[Ru]N3(CH=CHCO2Me)C2H(CO2Me)}[I] (8a) and the following cleavage of the Ru-N bond gives [Ru]-I and an organic triazole, N3(CH=CHCO2Me)C2H(CO2Me) (9a). A regiospecific alkylation happens by treatment of 3 with organic halides and gives a series of cationic N(1)-bound N(3)-alkylated-4-substituted triazolato complexes exclusively with high yields. The structures of 2, 3, 4, 5, (Z)-7, and 10a have been determined by single-crystal X-ray diffraction analysis.