C1-symmetrical cis-bis(di-2-pyridylamine)chloro(dimethyl sulfoxide-S)ruthenium(II) complex: Synthesis, crystal structure, and anion recognition using the NH groups in the chelating ligands

Toyama, Mari; Mishima, Daichi; Suganoya, Ryuji; Nagao, Noriharu

doi:10.1016/j.ica.2018.03.037

Cited by 7 publications

(26 citation statements)

References 54 publications

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“…The bond lengths and bond angles of the cationic part in our compound are similar to those of the neutral Hdpa 2,5,6 and of the bidentate Hdpa ligands in transition metal complexes, 1,3,4 but the conformation of H2dpa + is significantly different from those in the literature. In crystals of neutral Hdpa, two or four Hdpa molecules form intermolecular hydrogen-bridged dimers or tetramers, which are bound with some hydrogen bonding interactions between a pyridyl N atom and an H atom of an amino group of each Hdpa molecules (Figs.…”

supporting

confidence: 55%

“…1 They then also determined the crystal structure of uncoordinated Hdpa. 2 Up to now many chemists have revealed many crystal structures of transition metal complexes with Hdpa, 1,3,4 and a few crystal polymorphisms of uncoordinated Hdpa. 5,6 Moreover, about eighty crystal structures of compounds containing a protonated Hdpa cation, H2dpa + , 2-(pyridin-2-ylamino)pyridinium, are reported, such as (H2dpa)2[CoCl4] by F. A.…”

mentioning

confidence: 99%

“…On the other hand, all bidentate Hdpa ligands in transition metal complexes also are cisoid arrangements and bent conformations. 1,3,4 The dihedral angles of two pyridine rings of Hdpa are various in different complexes; [Cu(Hdpa)2]-(ClO4)2 (9.6 ) 1 , [CoCl2(Hdpa)] (5.6 ), 3 and cis-[RuCl(dmso-S)-(Hdpa)2]X (X = Cl or OTf, 24.8 -48.8 ). 4 These literature data show that the Hdpa molecule is very flexible and is able to have various dihedral angles, depending on the environment.…”

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confidence: 99%

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Crystal Structure of 2-(Pyridin-2-ylamino)pyridinium Trifluoromethanesulfonate

Toyama

Nagao

2021

X-ray Structure Analysis Online

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The crystal structure of a 2-(pyridin-2-ylamino)pyridinium trifluoromethanesulfonate, H2dpa(OTf ) (OTf -= CF3SO3 -), which consisted of a protonated 2-(pyridin-2-ylamino)pyridine (Hdpa) cation and a trifluoromethanesulfonate anion, was elucidated at 173 K by the single-crystal X-ray diffraction method. The compound crystallized in the monoclinic space group P21/m with a = 7.6770(4), b = 9.6170(5), c = 9.2748(5)Å, β = 106.201(6) , Z = 2, V = 657.56(6)Å 3 . The R1 and wR2 values were 0.0461 and 0.1223, respectively, for 1887 reflections.

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confidence: 55%

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confidence: 99%

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confidence: 99%

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Crystal Structure of 2-(Pyridin-2-ylamino)pyridinium Trifluoromethanesulfonate

Toyama

Nagao

2021

X-ray Structure Analysis Online

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“…Finally, treatment of 1 with two (or more) equivalents of N–N (or N–N′) leads to the replacement of all four dmso ligands, affording cis ‐ and/or trans ‐[RuCl 2 (N–N) 2 ] isomers, depending on the ligand and reaction conditions. In some cases, if the reaction is performed in the presence of DMSO, replacement of a chloride can occur with formation of complexes of the type [RuCl(dmso‐S)(N–N) 2 ]Cl …”

Section: Ru‐dmso Complexes As Precursorsmentioning

confidence: 99%

The Pivotal Role of Ru‐dmso Compounds in the Discovery of Well‐Behaved Precursors

Bratsos

Alessio

2018

Eur J Inorg Chem

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This paper is a tribute to the rich chemistry and great versatility of ruthenium-dmso precursors: over the years, from a handful of complexes we prepared literally hundreds of derivatives with all types of ligands, from mono-to polydentate, from pure σ-donors (e.g. NH 3 ) to phosphines and strong π-acceptors such as CO and NO. This systematic and extensive investigation had a thread of thought running through it: the identification of compounds that might have functional roles, either because they possess peculiar physical-chemical properties or [a]

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“… 59 , 60 However, there are examples in which the neutral diimines replace three DMSO ligands and a chloride, yielding cationic complexes of the type cis -[RuCl(L1) 2 (DMSO–S)]Cl. 61 , 62 …”

Section: Introductionmentioning

confidence: 99%

cis-Locked Ru(II)-DMSO Precursors for the Microwave-Assisted Synthesis of Bis-Heteroleptic Polypyridyl Compounds

et al. 2021

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We describe a synthetic strategy for the preparation of bis-heteroleptic polypyridyl Ru(II) complexes of the type [Ru(L1) 2 (L2)] 2+ (L1 and L2 = diimine ligands) from well-defined Ru(II) precursors. For this purpose, a series of six neutral, anionic, and cationic cis -locked Ru(II)-DMSO complexes ( 2 – 7 ) of the general formula [Y] fac -[RuX(DMSO–S) 3 (O–O)] n (where O–O is a symmetrical chelating anion: oxalate (ox), malonate (mal), acetylacetonate (acac); X = DMSO–O or Cl – ; n = −1/0/+1 depending on the nature and charge of X and O–O; when present, Y = K + or PF 6 – ) were efficiently prepared from the well-known cis -[RuCl 2 (DMSO) 4 ] ( 1 ). When treated with diimine chelating ligands (L1 = bpy, phen, dpphen), the compounds 2 – 7 afforded the target [Ru(L1) 2 (O–O)] 0/+ complex together with the undesired (and unexpected) [Ru(L1) 3 ] 2+ species. Nevertheless, we found that the formation of [Ru(L1) 3 ] 2+ can be minimized by carefully adjusting the reaction conditions: in particular, high selectivity toward [Ru(L1) 2 (O–O)] 0/+ and almost complete conversion of the precursor was obtained within minutes, also on a 100–200 mg scale, when the reactions were performed in absolute ethanol at 150 °C in a microwave reactor. Depending on the nature of L1 and concentration, with the oxalate and malonate precursors, the neutral product [Ru(L1) 2 (O–O)] can precipitate spontaneously from the final mixture, in pure form and acceptable-to-good yields. When spontaneous precipitation of the disubstituted product does not occur, purification from [Ru(L1) 3 ] 2+ can be rather easily accomplished by column chromatography or solvent extraction. By comparison, under the same conditions, compound 1 is much less selective, thus demonstrating that locking the geometry of the precursor through the introduction of O–O in the coordination sphere of Ru is a valid strategic approach. By virtue of its proton-sensitive nature, facile and quantitative replacement of O–O in [Ru(L1) 2 (O–O)] 0/+ by L2, selectively affording [Ru(L1) 2 (L2)] 2+ , was accomplished in refluxing ethanol in the presence of a slight excess of trifluoroacetic acid or HPF 6 .

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C1-symmetrical cis-bis(di-2-pyridylamine)chloro(dimethyl sulfoxide-S)ruthenium(II) complex: Synthesis, crystal structure, and anion recognition using the NH groups in the chelating ligands

Cited by 7 publications

References 54 publications

Crystal Structure of 2-(Pyridin-2-ylamino)pyridinium Trifluoromethanesulfonate

Crystal Structure of 2-(Pyridin-2-ylamino)pyridinium Trifluoromethanesulfonate

The Pivotal Role of Ru‐dmso Compounds in the Discovery of Well‐Behaved Precursors

cis-Locked Ru(II)-DMSO Precursors for the Microwave-Assisted Synthesis of Bis-Heteroleptic Polypyridyl Compounds

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