Reactivity oftrans-[PtX2(ketoxime)2] Complexes towardm-Chloroperoxybenzoic Acid:  An Efficient Route to Coordinated Nitrosoalkanes and Solvent Dependence of the Reaction

Kukushkin, Vadim Yu.; Tudela, David; Izotova, Youlia A.; Belsky, V. K.; Stash, A. I.

doi:10.1021/ic9600691

Cited by 24 publications

(20 citation statements)

References 45 publications

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“…Presumably, once the isopropylamine coordinates with the platinum atom, the complex is stable to cis-trans isomerisation. The ketoxime ligand maintains its structure through the reaction conditions, although it is known that the free ketoximes can be easily converted into nitroso compounds [21].…”

Section: Synthesis and Characterization Of The Cis And Trans Platinummentioning

confidence: 99%

Trans platinum complexes design: One novel water soluble oxime derivative that contains aliphatic amines in trans configuration

Quiroga

Cubo

Blas

et al. 2007

Journal of Inorganic Biochemistry

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In an attempt to design new antitumoral drugs based on transplatin complexes, we determined the experimental conditions for the preparation of trans-[Pt((CH(3))(2)CNOH)((CH(3))(2)CHNH(2))Cl(2)], and solved the crystal structure. The cytotoxicity of the novel complex, the cis counterpart, cisplatin, and a trans complex with aliphatic amines, as well as the capacity of some of these complexes to cause either apoptotic or necrotic cell death, was comparatively examined in NRK-52E rat renal tubular cells and HepG2 human hepatoma cells. The results indicate that the oxime complex with trans geometry, but not the one with cis geometry, causes death by apoptosis, making the complex potentially suitable for therapeutic purposes. However cytotoxicity values are higher in the case of cis geometry than in trans geometry in both tumoral and non-tumoral cell lines.

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Section: Synthesis and Characterization Of The Cis And Trans Platinummentioning

confidence: 99%

Trans platinum complexes design: One novel water soluble oxime derivative that contains aliphatic amines in trans configuration

Quiroga

Cubo

Blas

et al. 2007

Journal of Inorganic Biochemistry

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“…Moreover, apart from the data analyzed in the review, new interesting examples, e.g. stepwise deprotonation accompanied by self-assembly of oxime/oximato species formed, oxidation of coordinated oximes to give nitrosoalkanes, nitrosylation of metal centers, the redox duality of oxime species toward one and the same metal, observation of N−O bond cleavage in oxidative addition of oximes, and facile dehydration and formation of coordinated nitriles, have been reported in the last 3 years.…”

Section: Introductionmentioning

confidence: 99%

Iminoacylation. 1. Addition of Ketoximes or Aldoximes to Platinum(IV)-Bound Organonitriles

et al. 1998

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The metal-mediated iminoacylation reaction of ketoximes or aldoximes upon treatment with the organonitrile platinum(IV) complexes trans-[PtCl(4)(RCN)(2)] proceeds under relatively mild conditions in acetonitrile (R = Me) or in chloroform (R = CH(2)Ph, Ph) to give trans-[PtCl(4)(NH=C(R)ON=CR(1)R(2))(2)] (R(1) = R(2) = Me; R(1)R(2) = C(4)H(8), R(1)R(2) = C(5)H(10), R(1)R(2) = (H)Ph, R(1)R(2) = (H)C(6)H(4)(OH)-o; 1-14) in 90-95% yield. All these compounds were characterized by elemental analyses (C, H, N, Cl, Pt), FAB mass spectrometry, and IR and (1)H, (13)C{(1)H}, and (195)Pt NMR spectroscopies. X-ray structure determinations of [PtCl(4)(NH=C(Me)ON=CMe(2))(2)] (1) and [PtCl(4){NH=C(Me)ON=C(C(5)H(10))}(2)] (3) disclosed their overall trans-configuration and the amidine one-end rather than N,N-bidentate coordination mode of the N-donor ligands. The iminoacyl species are in E-conformation which is held by a rather weak N-H.N hydrogen bond between the amidine =NH atom and the oxime nitrogen with the following observed distances and angles for 1 and [3]: N(1).N(2), and N(1)-H, N(1)H.N(2) are 2.605 [2.592], 0.74 [0.71], and 2.20 [2.25] Å; N(1)-H.N(2) is 115 degrees [111 degrees ]. No evidence of the Z-conformation in solution was obtained by NMR spectroscopy. Compounds trans-[PtCl(4)(NH=C(R)ON=CR(1)R(2))(2)] are unexpectedly stable toward hydrolysis both in the solid state and in solutions.

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“…Indeed, the N(1)–O(1) and N(2)–O(3) bond distances are 1.364(7) and 1.367(7) Å (Figure ) and these values are close to N sp2 –O (1.394(18) Å in oximes) in bqoxH. The N(3)–O(3) and N(4)–O(4) bond lengths are 1.269(7) and 1.277(7) Å, and they are close to the NO bond length (1.265(5)–1.274(4) Å) in the radical-anion bqox •– ligands in the Ru II complexes, and smaller than the double NO bond (1.227(5)–1.243(3) Å in the Ru II -coordinated o -dinitrosobenze, 1.218(13) Å in the nitro group; ∼ 1.21 Å in metal-bound nitrosoalkanes − ). The C(1)–N(1) and C(2)–N(2) bond lengths are 1.309(8) and 1.318(8) Å in bqox and the C(7)–N(3) and C(8)–N(4) bond lengths are 1.372(8) and 1.380(8) Å in bqox •– , respectively.…”

Section: Resultsmentioning

confidence: 76%

The (Dioximate)Ni^II/I₂ System: Ligand Oxidation and Binding Modes of Triiodide Species

et al. 2020

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Reinvestigation of (o-benzoquinonedioximate)2Ni/I2 systems demonstrated that the reaction itself and also the crystallization conditions dramatically affect the identity of generated species. Crystallization (CHCl3, 20–25 °C) of the nickel(II) dioximate complex [Ni(bqoxH)2] (bqoxH2 = o-benzoquinonedioxime) with I2 in the 1:(1–10) molar ratios of the reactants led to several (o-benzoquinonedioximate)2Ni derivatives and/or iodine adducts [Ni(I)(bqoxH)(bqoxH2)]·3/2I2, [Ni(I3)(bqoxH)(bqoxH2)]·[Ni(bqoxH)2], and [Ni(I3)(bqox•–)(bqoxH2)]·I2; the latter one, featuring the anion-radical bqox•– ligand, is derived from the formal (−2H+/1e –)-oxidation of bqoxH2. In these three adducts, various types of noncovalent interactions were identified experimentally and their existence was supported theoretically. The [Ni(I3)(bqox•–)(bqoxH2)]·I2 adduct exhibits simultaneous semicoordination and coordination patterns of the triiodide ligand; this is the first recognition of the semicoordination of any polyiodide ligand to a metal center. The semicoordination noncovalent contact Ni···I3 (3.7011(10) Å) is substantially longer that the Ni–I3 coordination bond (2.8476(9) Å), and the difference in energies between these two types of linkages is 8–12 kcal/mol.

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Reactivity oftrans-[PtX₂(ketoxime)₂] Complexes towardm-Chloroperoxybenzoic Acid: An Efficient Route to Coordinated Nitrosoalkanes and Solvent Dependence of the Reaction

Cited by 24 publications

References 45 publications

Trans platinum complexes design: One novel water soluble oxime derivative that contains aliphatic amines in trans configuration

Trans platinum complexes design: One novel water soluble oxime derivative that contains aliphatic amines in trans configuration

Iminoacylation. 1. Addition of Ketoximes or Aldoximes to Platinum(IV)-Bound Organonitriles

The (Dioximate)Ni^II/I₂ System: Ligand Oxidation and Binding Modes of Triiodide Species

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Reactivity oftrans-[PtX2(ketoxime)2] Complexes towardm-Chloroperoxybenzoic Acid: An Efficient Route to Coordinated Nitrosoalkanes and Solvent Dependence of the Reaction

Cited by 24 publications

References 45 publications

Trans platinum complexes design: One novel water soluble oxime derivative that contains aliphatic amines in trans configuration

Trans platinum complexes design: One novel water soluble oxime derivative that contains aliphatic amines in trans configuration

Iminoacylation. 1. Addition of Ketoximes or Aldoximes to Platinum(IV)-Bound Organonitriles

The (Dioximate)NiII/I2 System: Ligand Oxidation and Binding Modes of Triiodide Species

Contact Info

Product

Resources

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Reactivity oftrans-[PtX₂(ketoxime)₂] Complexes towardm-Chloroperoxybenzoic Acid: An Efficient Route to Coordinated Nitrosoalkanes and Solvent Dependence of the Reaction

The (Dioximate)Ni^II/I₂ System: Ligand Oxidation and Binding Modes of Triiodide Species