Reactions of halogens with Pt(ii) complexes of N-alkyl- and N,N-dialkyl-N′-benzoylthioureas: oxidative addition and formation of an I2 inclusion compound

Westra, Arjan N.; Bourne, Susan A.; Esterhuysen, Catharine; Koch, Klaus

doi:10.1039/b503653d

Cited by 33 publications

(15 citation statements)

References 59 publications

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“…The axial positions of the Fe sites, which are collinear with the C 4 axis, are occupied by the bridging pyrazine ligands, which connect consecutive layers. The equatorial and axial Fe À N bond lengths are consistent with the LS and the HS states, respectively [Fe À N eq 1.940 (6) and Fe À N ax 2.001(12) at 293 K, and Fe À N eq 2.127 (8) and FeÀN ax 2.275(14) at 413 K]. The axial positions of the Pt centers, which are available in the so-called site B, are coordinated by two iodide anions with half occupancy.…”

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confidence: 83%

“…The Pt À I bond lengths [2.714(3) at 293 K and 2.702(3) at 413 K] are within the limits usually found for Pt À I complexes. [6] On the basis of the I/Pt ratio, the PtÀI distance, the occupancy of the I atoms, and the XPS data (see below), a reasonable "static" picture is represented by an alternate arrangement of square-planar [Pt II (CN) 4 ] 2À and axially elongated octahedral [Pt IV (CN) 4 (I) 2 ] 2À units in the framework ( Figure S1 in the Supporting Information). However, no extra X-ray diffraction peaks attributed to the super lattice based on ordered arrangement of the Pt II and Pt IV units were observed.…”

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confidence: 99%

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Oxidative Addition of Halogens on Open Metal Sites in a Microporous Spin‐Crossover Coordination Polymer

et al. 2009

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The last decade has witnessed a great activity in the realm of porous coordination polymers (PCPs). Their extreme chemical versatility and porosity has allowed chemists to consider PCPs as a new class of functional materials that are able to mimic, and even improve, the functions of zeolites, for example, storage, separation, and heterogeneous catalysis. [1] Furthermore, implementation of PCPs with solid-state properties (optical, magnetic, charge transport, etc.) would enable the expression of host-guest interactions in sorption and desorption processes in a sensory way as a response of the framework producing drastic physicochemical changes at ordinary temperatures. This almost unexplored strategy could provide a new generation of PCP-based sensors.[2]The chemo-responsive behavior of the Hofmann clathratePd, [3a] Pt [3a] ) based on the spin-crossover properties of the Fe II joints was recently demonstrated. The cooperative response mediated by the components of the framework confers bistable behavior to the solid at room temperature. These PCPs form a 3D pillared-layer-type porous framework consisting of cyano-bridged Fe II M II layers and pz pillar ligands, and adsorb various guest molecules. A bimodal reversible change of spin state at the Fe II sites was observed concomitantly with the uptake of guest molecules switching between the high-spin state (HS, yellow), stabilized by hydroxylic solvents and five-and six-membered aromatic molecules, and the low-spin state (LS, red-brown), stabilized by CS 2 (for M = Pt) [3a] or CH 3 CN (for M = Ni) [3b] at 298 K. In the framework, guest molecules can interact with the pyrazine pillar ligands (site A) and the M II centers (site B). One important feature not yet explored in these PCPs is the coordinative unsaturation of the M II centers. Incorporation of coordinatively unsaturated metal centers, so-called "open metal sites", may enhance the adsorptive selectivity for particular guest substances.[4] Herein we report the chemisorptive uptake of dihalogen molecules involving associative oxidation of Pt II to Pt IV and reduction of the dihalogen to the corresponding halide to give {Fe(pz) [Pt(CN)

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Oxidative Addition of Halogens on Open Metal Sites in a Microporous Spin‐Crossover Coordination Polymer

et al. 2009

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“…The new coordination mode of aroyl/acyllthiourea ligands along with the five different coordination modes was shown in Figure . Metal ions like Pt (II), Pd (II), Ru (II), Cu(I), Ag(I) and Au (III) coordinate with aroyl/acyl thiourea ligand via neutral monodentate fashion i.e ., through S only. But, here, it is relevant to mention that we have not been able to find a single example of a structurally well characterized metal‐thiourea complex in the literature, in which the aroyl/acylthiourea ligand is coordinated through S and N (monobasic bidentate) fashion as in scheme .…”

Section: Introductionmentioning

confidence: 99%

Unusual coordination mode of aroyl/acyl thiourea ligands and their π‐arene ruthenium (II) piano‐stool complexes: Synthesis, molecular geometry, theoretical studies and biological applications

Rohini

Konakanchi

Prashanth

et al. 2019

Applied Organom Chemis

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Two mononuclear ruthenium complexes (1 and 2) with aroyl/acylthiourea as an ancillary ligand of type, [(η6‐p‐cymene)RuCl(L‐N,S)], where [L1 = 2,4‐dichloro‐N‐(o‐tolylcarbamothioyl)benzamide] and L2 = N‐(phenylcarbamothioyl)cyclohexanecarboxamide] were synthesized and well characterized. The single crystal X‐ray diffraction studies revealed the coordination mode and the geometry of the complexes. The two complexes adopted general piano‐stool (three‐legged) geometry with a novel coordination mode of aroyl/acylthiourea through amide N (anionic) and thiocarbonyl S (neutral). This type of monobasic bidentate coordination of the aroyl/acylthiourea ligand was witnessed the first time around the metal ion. The coordination of the complexes was well explained through geometric parameters and frontier molecular orbital parameter values computed at the B3LYP/SDD level. The synthesized complexes were also screened for their antibacterial, antifungal, antioxidant and in vitro antiproliferative activities. Complexes exhibited good antimicrobial agents against various pathogens. The antioxidant activity of the complex 2 has shown most potent activity with IC50 value of 48.55 ± 1.7 μM compared to the reference drug. In addition, the in vitro antiproliferative activity of the complex 2 showed excellent activity against HepG‐2 cell line with the IC50 value of 24.30 ± 1.20 μM which is close to Doxorubicin standard drug.

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“…It turns out that these ligands are able to bind a wide variety of metal ions in different coordination modes, forming stable complexes. In most of the ones containing acyl thioureas, which were structurally characterized, they act as bidentate O,S-monoanionic ligands [19][20][21][22]. Also, it is well known that palladium(II) complexes are potential candidates to be used as metal based therapeutic agents, since this metal has a very similar chemistry to that of platinum(II), some of whose compounds are well known as anticancer agents [23].…”

Section: Introductionmentioning

confidence: 99%

On the cytotoxic activity of Pd(II) complexes of N,N-disubstituted-N′-acyl thioureas

Plutı́n

Mocelo

Alvarez

et al. 2014

Journal of Inorganic Biochemistry

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Reactions of halogens with Pt(ii) complexes of N-alkyl- and N,N-dialkyl-N′-benzoylthioureas: oxidative addition and formation of an I2 inclusion compound

Cited by 33 publications

References 59 publications

Oxidative Addition of Halogens on Open Metal Sites in a Microporous Spin‐Crossover Coordination Polymer

Oxidative Addition of Halogens on Open Metal Sites in a Microporous Spin‐Crossover Coordination Polymer

Unusual coordination mode of aroyl/acyl thiourea ligands and their π‐arene ruthenium (II) piano‐stool complexes: Synthesis, molecular geometry, theoretical studies and biological applications

On the cytotoxic activity of Pd(II) complexes of N,N-disubstituted-N′-acyl thioureas

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