Triruthenium and Triosmium Carbonyl Cluster Complexes Containing Deprotonated Di(2-pyridyl)amine in Unusual Coordination Modes

Cabeza, Javier A.; Rı́o, Ignacio del; Garcı́a-Granda, Santiago; Suárez, Marta

doi:10.1021/om020073m

Cited by 31 publications

(46 citation statements)

References 25 publications

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“…The one-electron nature of the couple is consistent with current height data, as compared to those of the oneelectron standard [Ru(bpy) 3 ] 2ϩ . More importantly exhaustive coulometric oxidation at 0.9 V afforded a coulomb count corresponding to a one-electron transfer ( Table 2).…”

Section: Electrochemistry: Metal Oxidationsupporting

confidence: 80%

“…Dichloromethane solutions of 2 are fluorescent at room temperature, the emission peak lying near 460 nm. The quantum yields (ϕ r ) are nearly one order of magnitude lower than that of the [Ru(bpy) 3 ] 2ϩ standard [33] ( Table 2). Excitation spectral studies have revealed that the emission is associated with the absorption band near 400 nm.…”

Section: Photophysical Propertiesmentioning

confidence: 88%

“…A representative case is shown in Figure 3. Assuming that the band has MLCT character, as suggested above, the possible involvement of the 3 MLCT state incorporating a π*(dmbi) contribution is implicated in the emission process. However, tris-biimidazole complexes of bivalent ruthenium are nonemitters at room temperature.…”

Section: Photophysical Propertiesmentioning

confidence: 90%

“…[10,11] The decarbonylative metallation of 4-methyl-2,6-diformylphenol by Ru(PPh 3 ) 3 Cl 2 in the presence of primary aromatic amines (RC 6 H 4 NH 2 ) furnishes organoruthenium species of the type Ru(η 2 -RL)(PPh 3 ) 2 (CO)Cl, (1), incorporating a four-membered chelate ring adjacent to a hydrogenbonded iminium-phenolato ring.…”

Section: Introductionmentioning

confidence: 99%

“…10 −3 and Յ 20 ns, respectively. The emission, which probably involves the 3 MLCT state incorporating a π* (dmbi) contribution, is peculiar to the coligation of η 1 -RL and dmbi to bivalent ruthenium. In dichloromethane solution 2 displays a quasireversible 2 + /2 couple near 0.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Structure, and Properties of Biimidazole‐Chelated Arylruthenium Complexes

2003

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By reacting Ru(η2‐RL)(PPh3)2(CO)Cl (1) with excess 4,5‐dimethyl‐2,2′‐biimidazole (dmbi), organometallics of the type [Ru(η1‐RL)(PPh3)2(CO)(dmbi)](PF6) (2) have been isolated in excellent yield (η2‐RL is C6H2O‐2‐CHNHC6H4R(p)‐3‐Me‐5, η1‐RL is C6H2OH‐2‐CHNC6H4R(p)‐3‐Me‐5 and R is Me, OMe and Cl). In this process the dmbi ligand undergoes five‐membered chelation, the iminium‐phenolato function tautomerizes to the imine‐phenol function and the Schiff base performs a large rotation around the Ru−C bond. The crystal and molecular structure of [Ru(η1‐MeL)(PPh3)2(CO)(dmbi)](PF6)·CH2Cl2 is reported. For steric reasons the carbon monoxide ligand is located syn to the phenolic oxygen atom as opposed to anti in the precursor 1. In the hydrogen bonded imine‐phenol function the O−H, H···N, and N···O distances are 0.83(8), 1.77(8), and 2.552(6) Å, respectively, the O−H···N angle being 156(2)°. The Ru(dmbi) chelate along with the metallated carbon atom and the CO ligand define an equatorial plane from which the metallated aldimine fragment is rotated by 34.5° due to interligand repulsion. This results in two unequal [2.348(2) and 2.411(2) Å] Ru−P bonds and an apparent suppression of the trans influence of the metallated carbanionic site. The cation and anion in the complex are engaged in N−H···F and C−H···F hydrogen bonding, generating a centrosymmetric dimer in the lattice. One of the hydrogen bonds, characterized by H···F, 2.03(8) Å and N−H···F, 166(2)°, is particularly strong. Solutions of 2 absorb near 400 nm and emit near 460 nm with quantum yields and lifetimes of ca. 10−3 and ⩽ 20 ns, respectively. The emission, which probably involves the 3MLCT state incorporating a π*(dmbi) contribution, is peculiar to the coligation of η1‐RL and dmbi to bivalent ruthenium. In dichloromethane solution 2 displays a quasireversible 2+/2 couple near 0.70 V vs. SCE [2+ is the ruthenium(III) analogue of 2]. Coulometrically generated solutions of 2+ display a strong absorption near 400 nm and rhombic EPR spectra with g values near 2.55, 2.15, and 1.83. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Section: Electrochemistry: Metal Oxidationsupporting

confidence: 80%

Section: Photophysical Propertiesmentioning

confidence: 88%

Section: Photophysical Propertiesmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis, Structure, and Properties of Biimidazole‐Chelated Arylruthenium Complexes

2003

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Di‐ and Trinuclear Ruthenium and Osmium Bis(2‐pyridyl) Ketone Oximate Derivatives

et al. 2003

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Treatment of [Ru3(CO)12] with bis(2‐pyridyl) ketone oxime (Hdpko) in refluxing THF leads to a separable mixture of [Ru3(μ,η3‐dpko‐N,N,O)2(CO)8] (1) and [Ru2(μ,η3‐dpko‐N,N,O)2(CO)4] (2). In both complexes, two Ru atoms are doubly bridged by two dpko ligands, which are attached to a Ru atom through the oximate O atom while chelating the other Ru atom through the N atoms of a pyridyl group and the oximate fragment. While the Ru−Ru distance of the bridged edge of complex 1 is very long [3.5388(9) Å], that of complex 2 is very short [2.620(1) Å]. The acetonitrile complexes [M3(CO)10(MeCN)2] (M = Ru, Os) react with Hdpko in THF at room temperature to give [M3(μ‐H)(μ,η3‐dpko‐N,N,O)(CO)9] [M = Ru (3) Os (4)], in which the dpko ligand behaves in the same way as in 1 and 2. The thermal reaction of 3 with Hdpko leads to a mixture of 1 and 2, while an analogous treatment of complex 4 gives [Os3(μ,η3‐dpko‐N,N,O)2(CO)8] (5), which is isostructural with complex 1. Compounds 1 and 3 are the first examples of ruthenium clusters containing oximate ligands. These oximate complexes display low activity as DNA cleavage agents, requiring high complex concentrations, long incubation times, and the use of UV light as a trigger. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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Persistence of a Ru₃(μ‐CO)₃(CO)₅Cluster Bound to a PNNP “Expanded Pincer” Ligand in Different Protonation States

et al. 2022

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We report the synthesis and characterization of Ru 3 (μ-CO) 3 (CO) 5 -type cluster complexes bound to a dinucleating PNNP 'expanded pincer' ligand. Each bidentate PN pocket of the ligand chelates a single ruthenium center of the cluster and can undergo deprotonation concomitant with dearomatization of its naphthyridine core. Although the cluster bearing a partially dearomatized ligand reacts with H 2 , we found no indication that this proceeds via a pathway involving metalligand cooperativity.

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Triruthenium and Triosmium Carbonyl Cluster Complexes Containing Deprotonated Di(2-pyridyl)amine in Unusual Coordination Modes

Cited by 31 publications

References 25 publications

Synthesis, Structure, and Properties of Biimidazole‐Chelated Arylruthenium Complexes

Synthesis, Structure, and Properties of Biimidazole‐Chelated Arylruthenium Complexes

Di‐ and Trinuclear Ruthenium and Osmium Bis(2‐pyridyl) Ketone Oximate Derivatives

Persistence of a Ru₃(μ‐CO)₃(CO)₅Cluster Bound to a PNNP “Expanded Pincer” Ligand in Different Protonation States

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Triruthenium and Triosmium Carbonyl Cluster Complexes Containing Deprotonated Di(2-pyridyl)amine in Unusual Coordination Modes

Cited by 31 publications

References 25 publications

Synthesis, Structure, and Properties of Biimidazole‐Chelated Arylruthenium Complexes

Synthesis, Structure, and Properties of Biimidazole‐Chelated Arylruthenium Complexes

Di‐ and Trinuclear Ruthenium and Osmium Bis(2‐pyridyl) Ketone Oximate Derivatives

Persistence of a Ru3(μ‐CO)3(CO)5Cluster Bound to a PNNP “Expanded Pincer” Ligand in Different Protonation States

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Persistence of a Ru₃(μ‐CO)₃(CO)₅Cluster Bound to a PNNP “Expanded Pincer” Ligand in Different Protonation States