Chemie polyfunktioneller Liganden, 57 [1] Über Iridium(I)- und Platin(II)-Komplexe des Bis(diphenylphosphino)amins und die oxidative Addition kleiner Moleküle an Di[bis(diphenylphosphino)amin-P.P']iricUum(I)-chlorid / Chemistry of Polyfunctional Ligands, 57[1] About Iridium(I) and Platinum(II) Complexes of Bis(diphenylphosphino)amine and the Oxidative Addition of Small Molecules to Di[bis(diphenylphosphino)amine]iridium(I)-chloride

1980 ◽  
Vol 35 (3) ◽  
pp. 307-315 ◽  
Author(s):  
Jochen Ellermann ◽  
Leo Mader
Keyword(s):  
Small Molecules ◽  
Nmr Spectra ◽  
Oxidative Addition ◽  
Molar Ratio ◽  
Ionic Complex ◽  
Oxidative Additions ◽  
Square Planar ◽  
Deuterated Derivative ◽  
New Compounds

R2PNHPR2 (1) (R = C6H5) reacts with [(μ-Cl)Ir(C8H12)]2 in a molar ratio of 4:1, to give the square planar, ionic complex [Ir(R2PNHPR2)2]Cl (2a). By reaction of 2a with NaBR4, [Ir(R2PNHPR2)2]BR4 (2b) is obtained. Treatment of 2 a with CO gives [Ir(CO)(R2PNHPR2)2]Cl (3a). The complex 3a is also formed by the reaction of 1 with Ir(CO)(PR3)2Cl (R = C6H5) and Ir(CO)2(p-H2N-C6H4-CH3)Cl. 3a undergoes metathesis with NH4PF6 to yield [Ir(CO)(R2PNHPR2)2]PF6 (3b). The N-deuterated derivative [Ir(CO)(R2PNDPR2)2]Cl (4) is made by H/D exchange from 3a with CH3OD. Oxidative additions of O2 , CS2, I2 and (SCN)2 to 2a yield [Ir(O2)(R2PNHPR2)2]Cl (5), [Ir(μ2-CS2)(R2PNHPR2)2]Cl (6), [Ir(I)2(R2PNHPR2)2]Cl (7) and [Ir(SCN)2(R2PNHPR2)2]Cl (8). Additionally K2[PtCl4] and 1 reacts to [Pt(R2PNHPR2)2]Cl2 (9). The new compounds are characterised, as far as possible, by their IR, FIR, Raman and 31P NMR spectra.

Chemie polyfunktioneller Liganden, 64 [1]. Über Hydridoiridium(III)-Komplexe des N.N-Bis(diphenylphosphino)-p-tolylamiii Chemistry of Polyfunctional Ligands, 64 [1]. On Hydridoiridium(III) Complexes of N,N-Bis(diphenylphosphino)-p-tolylamine

1981 ◽  
Vol 36 (5) ◽  
pp. 571-577 ◽  
Author(s):  
Jochen Ellermann ◽  
Leo Mader ◽  
Kurt Geibel
Keyword(s):  
Nmr Spectra ◽  
Oxidative Addition ◽  
H Nmr ◽  
New Compounds

H2 reacts with [Ir{(Ph2P)2N-p-C6H4CH3}2]Cl · 3 C6H6 (1) to give cis-[Ir(H)2{(Ph2P)2N-p-C6H4CH3}2]Cl · CH2Cl2 (2a). By reaction of 2a with NaBPh4 cis-[Ir(H)2{(Ph2P)2N-p-C6H4CH3}2]BPh4 (2 b) is obtained. Refluxing of 2a in CH2Cl2 yields trans-[lr(H)2{(Ph2P)2N-p-C6H4CH3}2]Cl · 1/2 CH2Cl2 (3a), which undegoes metatheses with NaBPh4 to trans-[Ir(H)2{(Ph2P)2N-p-C6H4CH3}2]BPh4 (3b). 3a is also formed by refluxing of 1 in methanol in the presence of oxygen. Oxidative addition of HCl to 1 and reaction with NaBPh4 yields trans-[Ir(H)(Cl){(Ph2P)2N-p-C6H4CH3}2]BPh4 (4b). The new compounds are characterised by their IR, Raman, 31P{1H} PFT and 1H NMR Spectra

scholarly journals Square-Planar vs. Trigonal Bipyramidal Geometry in Pt(II) Complexes Containing Triazole-Based Glucose Ligands as Potential Anticancer Agents

2021 ◽  
Vol 22 (16) ◽  
pp. 8704
Author(s):  
Alfonso Annunziata ◽  
Davide Liberti ◽  
Emiliano Bedini ◽  
Maria Elena Cucciolito ◽  
Domenico Loreto ◽  
...  
Keyword(s):  
Small Molecules ◽  
Anticancer Agents ◽  
Biological Action ◽  
Cytotoxic Action ◽  
Trigonal Bipyramidal ◽  
Square Planar ◽  
Overall Stability ◽  
Square Planar Complexes ◽  
New Compounds ◽  
Tumorigenic Cell

This article describes the synthesis, characterization, and biological activity of novel square-planar cationic platinum(II) complexes containing glucoconjugated triazole ligands and a comparison with the results obtained from the corresponding five-coordinate complexes bearing the same triazole ligands. Stability in solution, reactivity with DNA and small molecules of the new compounds were evaluated by NMR, fluorescence, and UV–vis absorption spectroscopy, together with their cytotoxic action against pairs of immortalized and tumorigenic cell lines. The results show that the square-planar species exhibit greater stability than the corresponding five-coordinate ones. Furthermore, although the square-planar complexes are less cytotoxic than the latter ones, they exhibit a certain selectivity. These results simultaneously demonstrate that overall stability is a fundamental prerequisite for preserving the performance of the agents and that coordinative saturation constitutes a point in favor of their biological action.

Bis[(2-diphenyIphosphino)phenyl]phenylphosphine as an Inflexible Tridentate Ligand for Indium Trichloride

1999 ◽  
Vol 54 (11) ◽  
pp. 1417-1419 ◽  
Author(s):  
Marcus Sigl ◽  
Annette Schier ◽  
Hubert Schmidbaur
Keyword(s):  
Spin System ◽  
Phosphorus Atom ◽  
Nmr Spectra ◽  
Lone Pair ◽  
Bidentate Ligand ◽  
Tridentate Ligand ◽  
Molar Ratio ◽  
X Ray Diffraction ◽  
Ionic Complex ◽  
X Ray

Anhydrous indium trichloride reacts with [2-(Ph2P)C6H4]2PPh (TP) in the molar ratio 2:1 to give an ionic complex [(TP)InCl2]+ InCL4- in almost quantitative yield. The structure of the product has been determined by a single crystal X-ray diffraction study. In the cation the TP molecule acts only as a bidentate ligand via its two terminal phosphorus atoms [In-P1 2.5956(8), In-P2 2.5799(7) Å], Although the central phosphorus atom is also rather close to the metal atom [2.8259(8) Å], the In-P3 interaction is inefficient because of an adverse orientation of the lone pair of electrons at P3 owing to the steric inflexibility of the ligand. Accordingly, the 31P NMR spectra of the compound in CD2CI2 show large contact shifts and quadrupole broadening only for the signals of the two terminal phosphorus atoms, whereas the lines of the central phosphorus atom are less shifted and well resolved (AB2 spin system at -60°C).

Crystal chemistry of high-Tc superconductors

1990 ◽  
Vol 48 (4) ◽  
pp. 1118-1119
Author(s):  
Maryvonne Hervieu
Keyword(s):  
Oxygen Deficiency ◽  
Large Family ◽  
Copper Oxides ◽  
High Tc Superconductors ◽  
High Tc ◽  
Single Mechanism ◽  
Square Planar ◽  
History Of ◽  
Bismuth Cuprates ◽  
New Compounds

Four years after the discovery of superconductivity at high temperature in the Ba-La-Cu-O system, more than thirty new compounds have been synthesized, which can be classified in six series of copper oxides: La2CuO4 - type oxides, bismuth cuprates, YBa2Cu3O7 family, thallium cuprates, lead cuprates and Nd2CuO4 - type oxides. Despite their quite different specific natures, close relationships allow their structures to be simply described through a single mechanism. The fifth first families can indeed be described as intergrowths of multiple oxygen deficient perovskite slabs with multiple rock salt-type slabs, according to the representation [ACuO3-x]m [AO]n.The n and m values are integer in the parent structures, n varying from 0 to 3 and m from 1 to 4; every member of this large family can thus be symbolized by [m,n]. The oxygen deficient character of the perovskite slabs involves the existence or the co-existence of several types of copper environment: octahedral, pyramidal and square planar.Both mechanisms, oxygen deficiency and intergrowth, are well known to give rise easily to nonstoichiometry phenomena. Numerous and various phenomena have actually been characterized in these cuprates, strongly depending on the thermal history of the samples.

scholarly journals Synthesis, Structure and In Vitro Anticancer Activity of Pd(II) Complex of Pyrazolyl-s-Triazine Ligand; A New Example of Metal-Mediated Hydrolysis of s-Triazine Pincer Ligand

Crystals ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 119
Author(s):  
Jamal Lasri ◽  
Matti Haukka ◽  
Hessa H. Al-Rasheed ◽  
Nael Abutaha ◽  
Ayman El-Faham ◽  
...  
Keyword(s):  
Thermal Conditions ◽  
Molar Ratio ◽  
Chloride Salt ◽  
Pincer Ligand ◽  
Hydrogen Bonding Interactions ◽  
Square Planar ◽  
Hirshfeld Analysis ◽  
Hydrolysis Of ◽  
Mcf 7

The square planar complex [Pd(PT)Cl(H2O)]*H2O (HPT: 6-(3,5-dimethyl-1H-pyrazol-1-yl)-1,3,5-triazine-2,4(1H,3H)-dione) was obtained by the reaction of 2-methoxy-4,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)-1,3,5-triazine (MBPT) pincer ligand with PdCl2 in a molar ratio (1:1) under thermal conditions and using acetone as a solvent. The reaction proceeded via C-N cleavage of one C-N moiety that connects the pyrazole and s-triazine combined with the hydrolysis of the O-CH3 group. The reaction of the chloride salt of its higher congener (PtCl2) gave [Pt(3,5-dimethyl-1H-pyrazole)2Cl2]. The crystal structure of [Pd(PT)Cl(H2O)]*H2O complex is stabilized by inter- and intra-molecular hydrogen bonding interactions. Hirshfeld analysis revealed that the H...H (34.6%), O...H (23.6%), and Cl...H (7.8%) interactions are the major contacts in the crystal. The charges at Pd, H2O, Cl and PT are changed to 0.4995, 0.2216, −0.4294 and −0.2917 instead of +2, 0, −1 and −1, respectively, using the MPW1PW91 method. [Pd(PT)Cl(H2O)]*H2O complex has almost equal activities against MDA-MB-231 and MCF-7 cell lines with IC50 of 38.3 µg/mL.

scholarly journals Reaktive E=C(p–p)π Systeme, XXXIV Addition von Alkoholen oder primären Aminen an Phosphaalkene F3CP=C(F)OR. Neue Trifluormethylphosphane und -phosphaalkene/Reactive E = C( p – p ) π-Systems, XXXIV Addition of Alcohols or Primary Amines to Phosphaalkenes F3CP= C(F)OR . Novel Trifluoromethylphosphanes and Phosphaalkenes

1993 ◽  
Vol 48 (1) ◽  
pp. 58-67 ◽  
Author(s):  
Joseph Grobe ◽  
Duc Le Van ◽  
Gudrun Lange
Keyword(s):  
High Resolution Mass Spectrometry ◽  
Molar Ratio ◽  
Primary Amines ◽  
The Novel ◽  
Experimental Conditions ◽  
Pull System ◽  
Fragment Ions ◽  
New Compounds ◽  
C Nmr

The course of the reactions o f fluorophosphaalkenes F3CP = C (F)OR [R = Me (1), Et (2)] with methanol or ethanol strongly depends on the experimental conditions. Thus at 70 °C a mixture of the 2-phosphapropionic acid ester F3CP (H )CO2R [R = Me (3), Et (4)] and trifluoromethylphosphane H2PCF3 is formed [molar ratio: 3 or 4 /H2 CF3 ≈1/1]. If the precursors F3CP (H )CO2R [R = Me (3), Et) are used as starting materials, the reaction with ROH under the same conditions affords 3 and 4, respectively, (90 to 95% yield) with only traces of H2PCF 3. In the presence o f iPr2NH these precursors react with R′OH to give the novel trifluoromethylphosphaalkenes F3CP = C (OR )OR [R /R′: Me/Me (6); E t/E t (7); Me/Et (8)]. With Et2NH , 3 undergoes an addition/elimination process yielding the interesting push/pull system Et2N(F)C = P-CO2Me (5). 1 and 2 react with primary amines R′NH2 (R′= tBu, Me) with stereoselective formation of the fairly labile phosphaalkenes F3CP = C(OR)NHR′ [R /R′: Me/tBu (9), Et/tBu(10), Me/Me (11)] with trans-positions for CF3 and NHR′.The new compounds 3 -11 were characterized by spectroscopic investigations (1H , 19F, 31P, 13C NMR ; IR, MS) and determination of M+ or typical fragment ions [M+ -OR ] by high resolution mass spectrometry.

Dihydroxy-4′,5 tétraméthoxy-2′,3,7,8 flavone, et hydroxy-5 pentaméthoxy-2′,3,4′,7,8 flavone, deux nouveaux composés naturels isolés de Notholaenaaffinis (Ptéridophytes)

1979 ◽  
Vol 57 (14) ◽  
pp. 1901-1902 ◽  
Author(s):  
Maurice Jay ◽  
Jean Favre-Bonvin ◽  
Eckhard Wollenweber
Keyword(s):  
Natural Products ◽  
Nmr Spectra ◽  
New Compounds

The structures 4′,5-dihydroxy-2′,3,7,8-tetramethoxyflavone and 5-hydroxy-2′,3,4′,7,8-penta-methoxyflavone have been attributed to two new compounds isolated from a farinose exudate of Notholaenaaffinis; this result is derived from uv, ms, and nmr spectra of the natural products and their derivatives.

scholarly journals Oxidative additions of alkynyl/vinyl iodides to gold and gold-catalyzed vinylation reactions triggered by the MeDalphos Ligand

2021 ◽  
Author(s):  
Jessica Rodriguez ◽  
Alexis Tabey ◽  
Sonia Ladeira ◽  
Didier Bourissou
Keyword(s):  
Oxidative Addition ◽  
Oxidative Additions ◽  
Vinyl Iodides

The hemilabile Ad2P(o-C6H4)NMe2 ligand promotes fast, quantitative and irreversible oxidative addition of alkynyl and vinyl iodides to gold. The reaction is general. It works with a broad range of substrates...

Synthese und Kristallstrukturen einiger Tetramethylstibonium-Hydrogendicarboxylate / Synthesis and Crystal Structures of Some Tetramethylstibonium Hydrogendicarboxylates

1982 ◽  
Vol 37 (11) ◽  
pp. 1393-1401 ◽  
Author(s):  
Beatrix Milewski-Mahrla ◽  
Hubert Schmidbaur
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Spectroscopic Data ◽  
Molar Ratio ◽  
Ionic Structure ◽  
X Ray Diffraction ◽  
X Ray ◽  
Carboxylate Oxygen ◽  
Donor Acceptor ◽  
New Compounds

Reactions of pentamethylantimony (CH3)5Sb with carboxylic acids in the molar ratio 1:2 afford one equivalent of methane and essentially quantitative yields of crystalline tetramothylstibonium hydrogendicarboxylates. Six new compounds of this series have been synthesized using benzoic, o-phthalic, salicylic, 4-ethoxy-salicylic, oxalic, and malic acid, and characterized by analytical and spectroscopic data. An ionic structure with strong hydrogen bonds in the anionic components is proposed.The crystal structures of the hydrogen-dibenzoato (1), hydrogen-ortho-plithalato (2) and 4-ethoxy-hydrogen-salicylate (3) were determined by single crystal X-ray diffraction. The compounds can be described as having ionic lattices with some donor-acceptor inter­actions between the stibonium centers and the carboxylate oxygen atoms. The anions are characterized by strong hydrogen bonds O...H...O. Thus, the (CH3)4Sb-tetrahedron in 1 is distorted by two benzoate oxygon atoms (at 304(2) and 340(2) pin). The cation in 2 is largely undistorted and the anion has a hydrogenphthalate hydrogen bond of d(O...H...O) = 232 pm. The cation-anion contact in 3 is as short as d(Sb-O) = 289 pm rendering the Sb atom pentacoordinate.

Bis[dicarbonyl(cyclopentadienyl)ruthenium(I)] Komplexe / Bis[dicarbonyl(cyclopentadienyl)ruthenium(I)] Complexes

2002 ◽  
Vol 57 (9) ◽  
pp. 1017-1026 ◽  
Author(s):  
Herbert Schumann ◽  
Susanne Stenz ◽  
Frank Girgsdies ◽  
Stefan H. Mühle
Keyword(s):  
Single Crystal ◽  
Nmr Spectra ◽  
X Ray ◽  
Tert Butyl ◽  
New Compounds ◽  
C Nmr

Ru3(CO)12 reacts with 1-tert-butyl-2,4-cyclopentadiene (1), 1-trimethylsilyl-2,4-cyclopentadiene (2), 1-tert-butyl-3-methyl-2,4-cyclopentadiene (3), 1,3-di(tert-butyl)-2,4-cyclopentadiene (4), 1-iso-propyl-2,3,4,5-tetramethyl-2,4-cyclopentadiene (5), 1-tert-butyl-2,3,4,5-tetramethyl- 2,4-cyclopentadiene (6), 1-phenyl-2,3,4,5-tetramethyl-2,4-cyclopentadiene (7), 2,5- diphenyl-2,4-cyclopentadiene (8), or 2,3,4,5-tetraphenyl-2,4-cyclopentadiene (9) with formation of the corresponding bis[dicarbonyl(cyclopentadienyl) ruthenium(I)] complexes [RuCp# (CO)2]2 1a to 9a. The 1H and 13C NMR spectra of the new compounds 3a and 5a to 9a as well as the single crystal X-ray structures of 1a, 4a, 5a, 7a, 8a, and 9a are reported and discussed

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